WO2019163859A1 - Photosensitive layer, laminate, photosensitive resin composition, kit, and production method for photosensitive resin composition - Google Patents
Photosensitive layer, laminate, photosensitive resin composition, kit, and production method for photosensitive resin composition Download PDFInfo
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- WO2019163859A1 WO2019163859A1 PCT/JP2019/006427 JP2019006427W WO2019163859A1 WO 2019163859 A1 WO2019163859 A1 WO 2019163859A1 JP 2019006427 W JP2019006427 W JP 2019006427W WO 2019163859 A1 WO2019163859 A1 WO 2019163859A1
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- Prior art keywords
- group
- photosensitive
- layer
- resin composition
- water
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 106
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 157
- 229920005989 resin Polymers 0.000 claims abstract description 157
- 239000002253 acid Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 24
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004090 dissolution Methods 0.000 claims abstract description 22
- 230000009471 action Effects 0.000 claims abstract description 19
- 230000005855 radiation Effects 0.000 claims abstract description 12
- 239000004065 semiconductor Substances 0.000 claims description 101
- 238000000034 method Methods 0.000 claims description 74
- 125000000217 alkyl group Chemical group 0.000 claims description 65
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 29
- 238000012545 processing Methods 0.000 claims description 15
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 10
- 230000003068 static effect Effects 0.000 claims description 9
- 206010034972 Photosensitivity reaction Diseases 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 230000036211 photosensitivity Effects 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
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- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
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Images
Classifications
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
Definitions
- the present invention relates to a photosensitive layer, a laminate, a photosensitive resin composition, a kit, and a method for producing the photosensitive resin composition.
- a device using an organic semiconductor has an advantage that it can be manufactured by a simple process as compared with a conventional device using an inorganic semiconductor such as silicon. Furthermore, the organic semiconductor can be easily changed in material properties by changing its molecular structure. In addition, there are a wide variety of materials, and it is thought that functions and elements that could not be achieved with inorganic semiconductors can be realized.
- Organic semiconductors can be applied to electronic devices such as organic solar cells, organic electroluminescence displays, organic photodetectors, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, information recording elements, etc. There is sex.
- Patent Document 1 discloses a laminate including a specific water-soluble resin layer and a photosensitive layer in this order on an organic semiconductor layer, and the water-soluble resin layer and the photosensitive layer are in contact with each other. Thus, it is described that a fine pattern by exposure and development of the photosensitive layer can be realized and cracks in the laminate can be suppressed.
- Patent Documents 2 and 3 are laminates having a water-soluble resin layer and a photosensitive layer on the surface of an organic semiconductor layer, and a specific photoacid generator and a specific resin are blended in the photosensitive resin composition. A laminate is disclosed. Thereby, it is described that a good pattern can be formed on the organic semiconductor.
- the protection of the organic semiconductor layer and the like can be ensured by interposing a water-soluble resin layer between the semiconductor layer such as the organic semiconductor layer and the photosensitive layer.
- the present inventors have made further improvements and focused on improving the production quality when the photosensitive layer is exposed and developed with respect to the photosensitive layer and the laminate including the photosensitive layer.
- a laminate in which an organic semiconductor layer 3, a water-soluble resin layer 2, and a photosensitive layer 11 are laminated in this order on a substrate 4 is prepared. (FIG. 3A).
- a removed portion (removal portion) 5 can be formed in the photosensitive layer (FIG.
- the present inventors have studied various materials and layer configurations and repeated improvement tests. As a result, it has been found that defects generated on the water-soluble resin layer can be suppressed or eliminated very effectively by adjusting the water content of the photosensitive resin composition forming the photosensitive layer.
- the present invention has been completed based on this discovery. That is, the above-mentioned problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 14>.
- ⁇ 3> The photosensitive layer according to ⁇ 1> or ⁇ 2>, wherein a static contact angle of the photosensitive resin composition on the polyvinyl alcohol film is 2 ° or more and 60 ° or less.
- ⁇ 4> The photosensitive layer according to any one of ⁇ 1> to ⁇ 3>, wherein the change in the dissolution rate due to the action of the acid of the resin in the photosensitive layer is a decrease in the dissolution rate.
- ⁇ 5> The photosensitive layer according to any one of ⁇ 1> to ⁇ 4>, wherein the resin in the photosensitive layer includes a polymer having a structural unit represented by the following formula (1);
- R 8 represents a hydrogen atom or an alkyl group
- L 1 represents a carbonyl group or a phenylene group
- R 1 to R 7 each independently represents a hydrogen atom or an alkyl group.
- ⁇ 7> The photosensitive layer according to any one of ⁇ 1> to ⁇ 6>, which is used for processing an organic semiconductor layer.
- ⁇ 8> A laminate having the photosensitive layer according to any one of ⁇ 1> to ⁇ 7> and a water-soluble resin layer.
- Photosensitive resin composition ⁇ 11> The photosensitive resin composition according to ⁇ 10>, which is used for processing an organic semiconductor layer.
- ⁇ 14> adjusting the water content of a composition comprising a compound that generates an acid upon irradiation with at least one of actinic rays and radiation, and a resin whose dissolution rate in butyl acetate is changed by the action of the acid, or Adjusting the water content of the raw material contained in the composition comprising a compound that generates an acid upon irradiation with at least one of actinic rays and radiation, and a resin that changes the dissolution rate in butyl acetate by the action of the acid, ⁇ 10 > Or ⁇ 11> The method for producing a photosensitive resin composition according to ⁇ 11>.
- the photosensitive layer, laminate, photosensitive resin composition, kit, and A method for producing a photosensitive resin composition when exposing and developing the photosensitive layer laminated on the upper side of the water-soluble resin layer, the photosensitive layer, laminate, photosensitive resin composition, kit, and A method for producing a photosensitive resin composition can be provided.
- the description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
- the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- active light in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
- light means actinic rays or radiation.
- exposure means not only exposure by far ultraviolet rays, X-rays, EUV light typified by mercury lamps and excimer lasers, but also drawing by particle beams such as electron beams and ion beams, unless otherwise specified.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- (meth) acrylate represents both and / or acrylate and methacrylate
- (meth) acryl represents both and / or acryl and “(meth) acrylic”
- "Acryloyl” represents both and / or acryloyl and methacryloyl.
- solid content concentration is the percentage of the mass of the other components excluding the solvent with respect to the total mass of the composition.
- “upper” and “lower” are described, they may be above or below the structure. That is, other structures may be interposed and do not need to be in contact with each other.
- the photosensitive layer side is referred to as the upper side
- the substrate or organic semiconductor layer side is referred to as the lower side.
- the photosensitive layer of the present invention is a photosensitive layer contained in a laminate having a water-soluble resin layer and a photosensitive layer, and is a compound that generates an acid upon irradiation with at least one of actinic rays and radiation (this compound is referred to herein).
- the water content in the photosensitive resin composition is 0.008% by mass or more and 1% by mass or less.
- the water content of the photosensitive resin composition By setting the water content of the photosensitive resin composition to the upper limit value or less, intermix (mixing between layers) can be suppressed and defects can be suppressed. On the other hand, it is considered that defects caused by metal impurities can be effectively suppressed by setting the water content to the lower limit value or more. That is, if the amount of water is too large, the photosensitive resin composition is likely to mix with the water-soluble resin layer and the interlayer (interface) to easily cause organic component defects (organic defects). However, in the present invention, water is not completely eliminated, but the water content of the photosensitive resin composition is set to an appropriate amount.
- water gently dissolves or disperses the metal impurities (inorganic defects) contained in the raw material such as the solvent, and the solvent includes the water in which the metal impurities are dissolved or dispersed. It is considered that it is dispersed throughout the photosensitive resin composition layer. As a result, it is possible to suppress the occurrence of inorganic component defects caused by metal impurities and the like. In other words, metal impurities and the like become cores and cause defects, but it is estimated that the defects could be suppressed or eliminated by gently dispersing them in the photosensitive resin composition by the action of water. .
- the photosensitive layer of the present invention is preferably used in combination with a water-soluble resin layer and disposed in contact with both.
- an organic semiconductor layer 3 is disposed on a substrate 4 as in the example shown in FIG.
- a water-soluble resin layer 2 that protects the organic semiconductor layer 3 is disposed on the surface in contact therewith.
- the photosensitive layer 1 is disposed thereon in contact with the water-soluble resin layer.
- the improved photosensitive layer 1 is formed, and even if this is exposed and developed with a predetermined mask, no defect occurs in the removal portion 5.
- the photosensitive layer of the present invention exhibits a particularly high effect when it is laminated on the water-soluble resin layer.
- FIG. 1B the improved photosensitive layer 1 is formed, and even if this is exposed and developed with a predetermined mask, no defect occurs in the removal portion 5.
- the form provided on the organic semiconductor layer is shown as an example.
- a water-soluble resin layer and a photosensitive layer may be used in combination on the surface of another material.
- the organic semiconductor layer is preferably used for processing.
- the laminate of the present invention is a laminate having the photosensitive layer of the present invention and a water-soluble resin layer, and preferably further includes an organic semiconductor layer, the organic semiconductor layer, the water-soluble resin layer, and the photosensitive layer. It is the laminated body laminated
- features of each layer and materials constituting the layer will be described.
- the organic semiconductor layer is a layer containing an organic material exhibiting semiconductor characteristics.
- a semiconductor made of an inorganic material there are a p-type organic semiconductor that conducts holes as carriers and an n-type organic semiconductor that conducts electrons as carriers.
- the ease of carrier flow in the organic semiconductor layer is represented by carrier mobility ⁇ . Although it depends on the application, in general, the mobility should be higher, preferably 10 ⁇ 7 cm 2 / Vs or more, more preferably 10 ⁇ 6 cm 2 / Vs or more, more preferably 10 ⁇ 5 cm 2 / Vs. More preferably, it is Vs or higher.
- the mobility can be obtained by characteristics when a field effect transistor (FET) element is manufactured or by a time-of-flight measurement (TOF) method.
- FET field effect transistor
- TOF time-of-flight measurement
- the organic semiconductor layer is preferably formed on a substrate as described above. That is, it is preferable to have a substrate on the surface of the organic semiconductor layer far from the water-soluble resin layer.
- the substrate include various materials such as silicon, quartz, ceramic, glass, polyester film such as polyethylene naphthalate (PEN) and polyethylene terephthalate (PET), and polyimide film. May be selected.
- PEN polyethylene naphthalate
- PET polyethylene terephthalate
- the thickness of the substrate is not particularly limited.
- any material of organic semiconductor materials may be used as long as it exhibits a hole (hole) transport property, but preferably a p-type ⁇ -conjugated polymer
- substituted or unsubstituted polythiophene for example, poly (3-hexylthiophene) (P3HT, Sigma Aldrich Japan GK), etc.
- polyselenophene polypyrrole, polyparaphenylene, polyparaphenylene vinylene, polythiophene vinylene, polyaniline Etc.
- condensed polycyclic compounds eg, substituted or unsubstituted anthracene, tetracene, pentacene, anthradithiophene, hexabenzocoronene, etc.
- triarylamine compounds eg, m-MTDATA (4,4 ′, 4 ′′) -Tris [(3-methylph nyl
- the n-type semiconductor material that can be used for the organic semiconductor layer may be any organic semiconductor material as long as it has an electron transporting property, but is preferably a fullerene compound, an electron-deficient phthalocyanine compound, or a naphthalene tetracarbonyl compound.
- the fullerene compound refers to a substituted or unsubstituted fullerene, and the fullerene is C 60 , C 70 , C 76 , C 78 , C 80 , C 82 , C 84 , C 86 , C 88 , C 90.
- C 96 , C 116 , C 180 , C 240 , C 540 fullerene and the like may be used, preferably substituted or unsubstituted C 60 , C 70 , C 86 fullerene, and particularly preferably PCBM ([6, 6] -Phenyl-C61-butyric acid methyl ester, Sigma-Aldrich Japan GK, etc.) and analogs thereof (substitute the C 60 moiety with C 70 , C 86, etc., the benzene ring of the substituent being another aromatic ring or Substituted with a heterocyclic ring, and methyl ester substituted with n-butyl ester, i-butyl ester, etc.).
- PCBM [6, 6] -Phenyl-C61-butyric acid methyl ester, Sigma-Aldrich Japan GK, etc.
- analogs thereof substitute the C 60 moiety with C 70 , C 86, etc., the benz
- Electron-deficient phthalocyanines are phthalocyanines of various central metals (F 16 MPc, FPc-S8, etc., in which four or more electron withdrawing groups are bonded, where M is a central metal, Pc is phthalocyanine, and S8 is ( n-octylsulfonyl group)), naphthalocyanine, anthracocyanine, substituted or unsubstituted tetrapyrazinoporphyrazine and the like.
- F 16 MPc, FPc-S8, etc. in which four or more electron withdrawing groups are bonded, where M is a central metal, Pc is phthalocyanine, and S8 is ( n-octylsulfonyl group)), naphthalocyanine, anthracocyanine, substituted or unsubstituted tetrapyrazinoporphyrazine and the like.
- naphthalene tetracarbonyl compound may be used, but naphthalene tetracarboxylic anhydride (NTCDA), naphthalene bisimide compound (NTCDI), and perinone pigment (Pigment Orange 43, Pigment Red 194, etc.) are preferable.
- NTCDA naphthalene tetracarboxylic anhydride
- NTCDI naphthalene bisimide compound
- perinone pigment Pigment Orange 43, Pigment Red 194, etc.
- Any perylene tetracarbonyl compound may be used, but perylene tetracarboxylic acid anhydride (PTCDA), perylene bisimide compound (PTCDI), and benzimidazole condensed ring (PV) are preferable.
- the TCNQ compound is a substituted or unsubstituted TCNQ and a benzene ring portion of TCNQ replaced with another aromatic ring or a heterocycle.
- TCNQ tetracyanoanthraquinodimethane
- TCN3T 2 , 2 '-((2E, 2 "E) -3', 4'-Alkyl substituted-5H, 5" H- [2,2 ': 5', 2 "-tertiophene] -5,5 ''-Diylidene) dimalononitrile derivative
- graphene is also included. Particularly preferred examples of the n-type organic semiconductor material are shown below.
- R in the formula may be any, but is a hydrogen atom, a substituted or unsubstituted, branched or straight chain alkyl group (preferably having 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8) and a substituted or unsubstituted aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 14 carbon atoms).
- Me is a methyl group.
- the organic material showing the characteristics of the semiconductor contained in the organic semiconductor layer may be one type or two or more types.
- the above materials are usually blended in a solvent, applied in layers on a substrate, dried and formed into a film.
- the solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, and 1-methylnaphthalene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Halogenated hydrocarbon solvents such as chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene; for example, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate; for example
- the ratio of the organic semiconductor in the composition for forming the organic semiconductor layer is preferably 0.1 to 80% by mass, more preferably 0.1 to 30% by mass. A film having a thickness can be formed.
- a resin binder may be blended in the composition for forming an organic semiconductor.
- the material for forming the film and the binder resin can be dissolved or dispersed in the above-mentioned appropriate solvent to form a coating solution, and the thin film can be formed by various coating methods.
- Resin binders include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyimide, polyurethane, polysiloxane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, polyethylene, polypropylene, and other insulating polymers, and their co-polymers.
- Examples thereof include photoconductive polymers such as coalescence, polyvinyl carbazole and polysilane, and conductive polymers such as polythiophene, polypyrrole, polyaniline and polyparaphenylene vinylene.
- the resin binder may be used alone or in combination. In consideration of the mechanical strength of the thin film, a resin binder having a high glass transition temperature is preferable, and in consideration of charge mobility, a resin binder made of a photoconductive polymer or a conductive polymer having a structure containing no polar group is preferable.
- the blending amount is preferably 0.1 to 30% by mass in the organic semiconductor layer. Only one type of resin binder may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
- a single layer or a mixed solution to which various semiconductor materials and additives are added may be applied onto a substrate or the like to form a blend film composed of a plurality of material types. For example, when a photoelectric conversion layer is manufactured, a mixed solution with another semiconductor material can be used. In film formation, the substrate may be heated or cooled, and the film quality and packing of molecules in the film can be controlled by changing the temperature of the substrate.
- the temperature of the substrate is not particularly limited, but is preferably ⁇ 200 ° C. to 400 ° C., more preferably ⁇ 100 ° C. to 300 ° C., and further preferably 0 ° C. to 200 ° C.
- the characteristics of the formed organic semiconductor layer can be adjusted by post-processing. For example, it is possible to improve the characteristics by changing the film morphology and the molecular packing in the film by exposing to a heat treatment or a vaporized solvent. Further, by exposing to an oxidizing or reducing gas, solvent, substance, or the like, or mixing them, an oxidation or reduction reaction can be caused to adjust the carrier density in the film.
- the thickness of the organic semiconductor layer is not particularly limited and varies depending on the type of electronic device used, but is preferably 5 nm to 50 ⁇ m, more preferably 10 nm to 5 ⁇ m, and still more preferably 20 nm to 500 nm.
- the water-soluble resin layer preferably contains a water-soluble resin and is formed from a water-soluble resin composition.
- the water-soluble resin refers to a resin in which the amount of dissolved resin with respect to 100 g of water at 20 ° C. is 1 g or more, preferably 5 g or more, more preferably 10 g or more, and further preferably 30 g or more. preferable. There is no upper limit, but it is practical to be 20 g.
- water-soluble resin examples include polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), water-soluble polysaccharides (water-soluble cellulose (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, etc. ), Pullulan or a pullulan derivative, starch, hydroxypropyl starch, carboxymethyl starch, chitosan, cyclodextrin), polyethylene oxide, polyethyloxazoline and the like.
- PVP and PVA are preferable, and PVA is more preferable. Of these, two or more different main chain structures may be selected and used, or may be used as a copolymer.
- the weight average molecular weight of the water-soluble resin is not particularly limited, but the weight average molecular weight of the polyvinylpyrrolidone used in the present invention is preferably 50,000 to 400,000.
- the weight average molecular weight of the polyvinyl alcohol used in the present invention is preferably 15,000 to 100,000. For other resins, it is preferably in the range of 10,000 to 300,000.
- the dispersity (weight average molecular weight / number average molecular weight) of the water-soluble resin (PVP, PVA) used in the present invention is preferably 1.0 to 5.0, more preferably 2.0 to 4.0.
- the content of the water-soluble resin in the water-soluble resin composition may be appropriately adjusted as necessary, but is preferably 30% by mass or less, more preferably 25% by mass or less, and 20% by mass or less. More preferably it is. As a minimum, it is preferred that it is 1 mass% or more, it is more preferred that it is 2 mass% or more, and it is still more preferred that it is 4 mass% or more.
- the thickness of the water-soluble resin layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, further preferably 1.0 ⁇ m or more, and further preferably 2.0 ⁇ m or more.
- As an upper limit of the thickness of a water-soluble resin layer 10 micrometers or less are preferable, 5.0 micrometers or less are more preferable, and 3.0 micrometers or less are further more preferable.
- the water-soluble resin layer can be formed, for example, by applying a water-soluble resin composition containing one or more of the above water-soluble resins on the organic semiconductor layer and drying it.
- the water-soluble resin composition contains water as a solvent and may further contain other additives.
- the solid content concentration of the water-soluble resin composition is preferably 0.5 to 30% by mass, more preferably 1.0 to 20% by mass, and further preferably 2.0 to 14% by mass. preferable. It can apply
- Application is preferred as the application method.
- application methods include slit coating, casting, blade coating, wire bar coating, spray coating, dipping (dip) coating, bead coating, air knife coating, curtain coating, ink jet, Examples thereof include a spin coating method and a Langmuir-Blodgett (LB) method. It is more preferable to use a casting method, a spin coating method, and an ink jet method. Such a process makes it possible to produce a water-soluble resin layer having a smooth surface and a large area at a low cost.
- LB Langmuir-Blodgett
- the water-soluble resin composition preferably further contains a surfactant for improving coatability.
- a surfactant any surfactant such as nonionic, anionic, and amphoteric fluorine may be used as long as it reduces the surface tension.
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and other polyoxyethylene alkyl ethers.
- Oxyethylene alkyl aryl ethers such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, etc.
- Sorbitan alkyl esters such as glyceride alkyl esters such as glycerol monostearate and glycerol monooleate
- Nonionic surfactants such as oligomers containing fluorine or silicon, acetylene glycol, ethylene oxide adducts of acetylene glycol, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, sodium butyl naphthalene sulfonate, pentyl naphthalene sulfonic acid
- Alkyl naphthalene sulfonates such as sodium, sodium hexyl naphthalene sulfonate, sodium octyl naphthalene sulfonate
- alkyl sulfates such as sodium lauryl sulfate
- alkyl sulfonates such as sodium dodecyl sul
- the addition amount of the surfactant is preferably 0.001 to 20% by mass, more preferably 0.001 to 5% by mass, and still more preferably 0% in the solid content. .01 to 1% by mass.
- These surfactants may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the photosensitive layer of the present invention is a layer formed from a photosensitive resin composition containing an acid generator, an acid-reactive resin, and water.
- the photosensitive resin composition forming the photosensitive layer contains water.
- the amount of water contained in the photosensitive resin composition is defined as 0.008% by mass or more, preferably 0.009% by mass or more, and more preferably 0.01% by mass or more.
- the upper limit is regulated to 1% by mass or less, preferably 0.8% by mass or less, more preferably 0.7% by mass or less, and may be 0.05% by mass or less.
- Adjustment of the water content in the photosensitive resin composition may be carried out by a conventional method. For example, adjusting the water content of a composition containing an acid generator and an acid-reactive resin, or adjusting the water content of a raw material contained in a composition containing an acid generator and an acid-reactive resin The manufacturing method of the photosensitive resin composition containing this is mentioned.
- the weight average molecular weight of the acid-reactive resin in the photosensitive layer is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 35,000 or more.
- the upper limit is not particularly defined, but is preferably 100,000 or less, may be 70,000 or less, and may be 50,000 or less.
- the amount of the component having a weight average molecular weight of 1,000 or less contained in the acid-reactive resin is preferably 10% by mass or less, more preferably 5% by mass or less of the total acid-reactive resin component. By setting it as such a structure, the sensitivity fluctuation between resin production lots can be reduced more effectively.
- the dispersity (weight average molecular weight / number average molecular weight) of the acid-reactive resin is preferably 1.0 to 4.0, more preferably 1.1 to 2.5.
- the photosensitive resin composition forming the photosensitive layer may contain a solvent.
- An embodiment in which the amount of the solvent contained in the photosensitive resin composition is 1 to 10% by mass is exemplified.
- the photosensitive layer is preferably a chemically amplified photosensitive layer. When the photosensitive layer is of a chemical amplification type, high storage stability and fine pattern formation can be achieved.
- the content of the acid reactive resin in the photosensitive layer is preferably 20 to 99.9% by mass, more preferably 40 to 99% by mass, and further preferably 70 to 99% by mass. 1 type, or 2 or more types of acid reactive resin may be contained. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the photosensitive layer is preferably hardly soluble in a developing solution containing an organic solvent in the exposed portion. Slightly soluble means that the exposed portion is hardly soluble in the developer, and specifically, 50 mJ / cm at least one of a wavelength of 365 nm (i-line), a wavelength of 248 nm (KrF line) and a wavelength of 193 nm (ArF line).
- the polarity changes as described above by exposing at a dose of 50 to 250 mJ / cm 2 at at least one of a wavelength of 365 nm (i-line), a wavelength of 248 nm (KrF line) and a wavelength of 193 nm (ArF line). Is more preferable.
- the photosensitive layer may be a negative photosensitive layer or a positive photosensitive layer, but a negative photosensitive layer is preferable because it enables formation of finer trenches and hole patterns. . Furthermore, the negative photosensitive layer can more effectively suppress organic defects.
- the thickness of the photosensitive layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, further preferably 0.75 ⁇ m or more, and particularly preferably 0.8 ⁇ m or more from the viewpoint of improving the resolution.
- the upper limit of the thickness of the photosensitive layer is preferably 10 ⁇ m or less, more preferably 5.0 ⁇ m or less, and further preferably 2.0 ⁇ m or less.
- the total thickness of the photosensitive layer and the water-soluble resin layer is preferably 0.2 ⁇ m or more, more preferably 1.0 ⁇ m or more, and further preferably 2.0 ⁇ m or more.
- the upper limit is preferably 20.0 ⁇ m or less, more preferably 10.0 ⁇ m or less, and even more preferably 5.0 ⁇ m or less.
- the photosensitive layer preferably has photosensitivity to i-ray irradiation.
- Photosensitivity is a property in which a material is altered by irradiation with at least one of actinic rays and radiation (if it has photosensitivity to i-ray irradiation, i-ray irradiation). This alteration is accompanied by a change in the dissolution rate with respect to butyl acetate.
- the photosensitive resin composition is preferably a chemically amplified photosensitive resin composition containing at least an acid reactive resin and a photoacid generator.
- the acid-reactive resin is a resin component constituting the photosensitive resin composition, and the dissolution rate in butyl acetate is changed by the action of an acid.
- the acid-reactive resin in the present invention is usually a resin containing a structural unit containing a group dissociated by an acid, and may contain another structural unit.
- the acid-reactive resin is a resin whose dissolution rate with respect to butyl acetate is changed by the action of an acid, and this change is more preferably a decrease in the dissolution rate.
- the dissolution rate of the acid-reactive resin in an organic solvent having an sp value of 18.0 (MPa) 1/2 or less is more preferably 40 nm / second or more.
- the dissolution rate in an organic solvent having an sp value of 18.0 (MPa) 1/2 or less is more preferably less than 1 nm / second.
- the acid-reactive resin is also soluble in an organic solvent having an sp value (solubility parameter value) of 18.0 (MPa) 1/2 or less, and tetrahydrofuranyl in a structural unit represented by the following formula (1)
- a resin that is hardly soluble in an organic solvent having a sp value of 18.0 (MPa) 1/2 or less when the group is decomposed or dissociated is preferable.
- sp value (solubility parameter value) is 18.0 (MPa) soluble in an organic solvent of 1/2” or less means that a solution of a compound (resin) is applied on a substrate, and then at 100 ° C. for 1 minute.
- the dissolution rate of the coating film (thickness 1 ⁇ m) of the compound (resin) formed by heating with respect to butyl acetate at 23 ° C. is 20 nm / second or more, and the “sp value is 18.0 (MPa ) “Slightly soluble in 1/2 or less organic solvent” means that a compound (resin) coating film (thickness) is formed by applying a compound (resin) solution on a substrate and heating at 100 ° C. for 1 minute. 1 ⁇ m) at 23 ° C. is less than 10 nm / second.
- the acid-reactive resin is preferably an acrylic polymer.
- “Acrylic polymer” is an addition polymerization type resin, which is a polymer containing a structural unit derived from (meth) acrylic acid or an ester thereof, and other than a structural unit derived from (meth) acrylic acid or an ester thereof. These structural units may include, for example, structural units derived from styrenes, structural units derived from vinyl compounds, and the like.
- the acrylic polymer preferably has a structural unit derived from (meth) acrylic acid or an ester thereof in an amount of 50 mol% or more, more preferably 80 mol% or more, based on all the structural units in the polymer. Particularly preferred is a polymer consisting only of structural units derived from (meth) acrylic acid or its ester. Such an acrylic polymer is preferably used for negative development.
- the acrylic polymer has a structural unit containing a protected carboxyl group or a protected phenolic hydroxyl group.
- the monomer capable of forming a structural unit containing a protected carboxyl group include (meth) acrylic acid protected with an acid dissociable group.
- Preferred examples of the monomer having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and ⁇ -methyl-p-hydroxystyrene. Specific examples include compounds described in [0158] to [0221] of Japanese Patent No. 4895376. Among these, ⁇ -methyl-p-hydroxystyrene is more preferable.
- the acid-reactive resin preferably has a cyclic ether ester structure, and more preferably has a structure represented by the following formula (1).
- R 8 represents a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3)
- L 1 represents a carbonyl group or a phenylene group
- R 1 R 7 each independently represents a hydrogen atom or an alkyl group.
- R 8 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
- L 1 represents a carbonyl group or a phenylene group, and is preferably a carbonyl group.
- R 1 to R 7 each independently represents a hydrogen atom or an alkyl group.
- the alkyl group in R 1 to R 7 has the same meaning as R 8 , and the preferred embodiment is also the same. Further, among the R 1 ⁇ R 7, preferably more than one is a hydrogen atom, it is more preferable that all of R 1 ⁇ R 7 are hydrogen atoms.
- (1-1) and (1-2) are particularly preferable.
- the radical polymerizable monomer used for forming the structural unit (1) a commercially available one may be used, or one synthesized by a known method may be used. For example, it can be synthesized by reacting (meth) acrylic acid with a dihydrofuran compound in the presence of an acid catalyst. Alternatively, it can be formed by reacting a carboxyl group or a phenolic hydroxyl group with a dihydrofuran compound after polymerization with a precursor monomer.
- Examples of the structural unit containing a protected phenolic hydroxyl group include the structural unit represented by the following formula (2).
- A represents a hydrogen atom or a group capable of leaving by the action of an acid.
- Examples of the group capable of leaving by the action of an acid include an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3), and an alkoxyalkyl group (preferably having 2 to 12 carbon atoms and 2 To 6 are more preferred, and 2 to 3 are more preferred), an aryloxyalkyl group (preferably having a total carbon number of 7 to 40, more preferably 7 to 30 and even more preferably 7 to 20), an alkoxycarbonyl group (having 2 carbon atoms).
- A may further have a substituent.
- R 10 represents a substituent.
- R 9 represents a group having the same meaning as R 8 in Formula (1).
- nx represents an integer of 0 to 3.
- group dissociating by an acid among the compounds described in paragraphs 0039 to 0049 of JP-A-2008-197480, a structural unit having a group dissociating by an acid is preferable, and JP-A-2012-159830 ( The compounds described in paragraph Nos. 0052 to 0056 of Japanese Patent No. 5191567) are also preferable, the contents of which are incorporated herein.
- the proportion of the structural unit (1) and the structural unit (2) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and further preferably 10 to 60 mol%.
- the acrylic polymer may contain only 1 type of structural unit (1), or may contain 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the acrylic polymer may contain a structural unit having a crosslinkable group. Details of the crosslinkable group can be referred to the descriptions in paragraph numbers 0032 to 0046 of JP2011-209692A, the contents of which are incorporated herein.
- the acid-reactive resin may have a configuration that does not substantially contain the structural unit (3) having a crosslinkable group. preferable. With such a configuration, the photosensitive layer can be more effectively removed after patterning.
- “substantially” means, for example, 3 mol% or less, preferably 1 mol% or less of all structural units of the acid-reactive resin.
- the acid-reactive resin may contain other structural units (structural unit (4)).
- structural unit (4) examples of the radical polymerizable monomer used for forming the structural unit (4) include compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623.
- structural unit (4) a structural unit derived from at least one selected from the group consisting of a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene, and an N-substituted maleimide. Is mentioned.
- hydrophobic monomers are preferred.
- the structural unit (4) can be used alone or in combination of two or more.
- the content of the monomer unit forming the structural unit (4) in the case where the structural unit (4) is included in all monomer units constituting the acrylic polymer is preferably 1 to 60 mol%, and 5 to 50 mol%. Is more preferable, and 5 to 40 mol% is more preferable. When using 2 or more types, it is preferable that a total amount becomes the said range.
- radical polymerizable monomers used to form at least the structural unit (1), the structural unit (2), etc. can be synthesized by polymerizing a radically polymerizable monomer mixture containing a radical polymerization initiator in an organic solvent.
- the acid-reactive resin 2,3-dihydrofuran is added at room temperature (in the absence of an acid catalyst) to the acid anhydride group in the precursor copolymer obtained by copolymerizing unsaturated polyvalent carboxylic acid anhydrides.
- a copolymer obtained by addition at a temperature of about 25 ° C. to 100 ° C. is also preferable.
- the following resins are also listed as preferred examples of the acid-reactive resin.
- BzMA / THFMA / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
- BzMA / THFAA / t-BuMA (molar ratio: 20 to 60:35 to 65: 5 to 30)
- BzMA / THPMA / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
- BzMA / PEES / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
- BzMA is benzyl methacrylate
- THFMA is tetrahydrofuran-2-yl methacrylate
- BuMA is butyl methacrylate
- THFAA is tetrahydrofuran-2-yl acrylate
- THPMA is tetrahydro-2H-pyran-2.
- PEES is p-ethoxyethoxystyrene.
- Examples of the acid-reactive resin used for positive development include those described in JP2013-011678A, the contents of which are incorporated herein.
- the content of the acid-reactive resin in the photosensitive resin composition is preferably 20 to 99% by mass and more preferably 40 to 99% by mass with respect to the total solid content of the photosensitive resin composition. Preferably, it is 70 to 99% by mass. When the content is within this range, the pattern formability upon development is good.
- the acid-reactive resin may contain only 1 type, and may contain 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the photosensitive resin composition may contain a photoacid generator.
- the photoacid generator is preferably a photoacid generator having absorption at a wavelength of 365 nm.
- the photoacid generator is preferably a compound having an oxime sulfonate group (hereinafter also simply referred to as an oxime sulfonate compound).
- the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group. However, the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS- It is preferable that it is an oxime sulfonate compound represented by 105).
- X 3 represents an alkyl group, an alkoxyl group, or a halogen atom. When a plurality of X 3 are present, they may be the same or different.
- the alkyl group and alkoxyl group in X 3 may have a substituent.
- the alkyl group in X 3 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
- the alkoxyl group in X 3 is preferably a linear or branched alkoxyl group having 1 to 4 carbon atoms.
- the halogen atom in X 3 is preferably a chlorine atom or a fluorine atom.
- m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, the plurality of X 3 may be the same or different.
- R 34 represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxyl group having 1 to 5 carbon atoms.
- W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxyl group having 1 to 5 carbon atoms.
- m3 is 3
- X 3 is a methyl group
- the substitution position of X 3 is an ortho position
- R 34 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2
- a compound which is an -oxonorbornylmethyl group or a p-toluyl group is particularly preferable.
- oxime sulfonate compound represented by the formula (OS-1) include the following compounds described in paragraph numbers 0064 to 0068 of JP2011-209692A, the contents of which are described in the present specification. Incorporated into.
- R 11 represents an alkyl group, an aryl group, or a heteroaryl group
- a plurality of R 12 s that may be present each independently represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom
- a plurality of R 16 s that may be present Each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
- X represents O or S
- ns represents 1 or 2
- ms represents 0 to 6 Represents an integer.
- the alkyl group, aryl group or heteroaryl group represented by R 11 may have a substituent.
- the alkyl group represented by R 11 is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
- Examples of the substituent that the alkyl group represented by R 11 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Is mentioned.
- alkyl group represented by R 11 examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, and n-hexyl.
- the aryl group represented by R 11 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
- Examples of the substituent that the aryl group represented by R 11 may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Examples thereof include an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.
- the aryl group represented by R 11 is preferably a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
- the heteroaryl group represented by R 11 is preferably a heteroaryl group having 4 to 30 carbon atoms which may have a substituent.
- Examples of the substituent that the heteroaryl group represented by R 11 may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, and an aryloxycarbonyl group. , An aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.
- the heteroaryl group represented by R 11 only needs to have at least one heteroaromatic ring. For example, the heteroaromatic ring and the benzene ring may be condensed.
- heteroaryl group represented by R 11 examples include a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring, which may have a substituent.
- a group obtained by removing one hydrogen atom from a ring selected from the group consisting of:
- R 12 is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
- R 12 which may be present in the compound in two or more, one or two are preferably an alkyl group, an aryl group or a halogen atom, more preferably one is an alkyl group, an aryl group or a halogen atom. It is particularly preferred that one is an alkyl group and the rest are hydrogen atoms.
- the alkyl group or aryl group represented by R 12 may have a substituent. Examples of the substituent that the alkyl group or aryl group represented by R 12 may have include the above W.
- the alkyl group represented by R 12 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and an alkyl group having 1 to 6 carbon atoms which may have a substituent. More preferably, it is a group.
- Examples of the alkyl group represented by R 12 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, A chloromethyl group, a bromomethyl group, a methoxymethyl group, and a benzyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group.
- a group is more preferable, a methyl group, an ethyl group, an n-propyl group, an n-butyl group and an n-hexyl group are more preferable, and a methyl group is particularly preferable.
- the aryl group represented by R 12 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
- the aryl group represented by R 12 is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
- halogen atom represented by R 12 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.
- X represents O or S, and is preferably O.
- the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
- ns represents 1 or 2, and when X is O, ns is preferably 1, and when X is S, ns is preferably 2.
- the alkyl group and alkyloxy group represented by R 16 may have a substituent.
- the alkyl group represented by R 16 is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent. Examples of the substituent that the alkyl group represented by R 16 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Is mentioned.
- Examples of the alkyl group represented by R 16 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, and n-hexyl. Group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group and benzyl group are preferred.
- the alkyloxy group represented by R 16 is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent.
- alkyloxy group represented by R 16 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl.
- the alkyloxy group represented by R 16 is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group.
- Examples of the aminosulfonyl group for R 16 include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group.
- Examples of the alkoxysulfonyl group represented by R 16 include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.
- ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.
- the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), (OS-110) or (OS-111).
- the compound represented by OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108). ) Or (OS-109) is particularly preferable.
- R 11 represents an alkyl group, an aryl group or a heteroaryl group
- R 17 represents a hydrogen atom or a bromine atom
- R 18 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl Group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group
- R 19 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group
- R 20 represents a hydrogen atom or a methyl group.
- R 17 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
- R 18 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and an alkyl group having 1 to 8 carbon atoms
- a halogen atom or a phenyl group is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is further preferable, and a methyl group is particularly preferable.
- R 19 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
- R 20 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
- the oxime steric structure (E, Z) may be either one or a mixture.
- Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include the compounds described in paragraph numbers 0088 to 0095 of JP 2011-209692 A, and their contents Are incorporated herein.
- oxime sulfonate compound having at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
- R 11 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group.
- R 11 is a cyano group or an aryl group is more preferable, and an embodiment in which R 11 is a cyano group, a phenyl group, or a naphthyl group is more preferable.
- R 12a represents an alkyl group or an aryl group.
- X is, -O -, - S -, - NH -, - NR 15 -, - CH 2 -, - CR 16 H- or -CR 16 R 17 - represents, in each of R 15 ⁇ R 17 independently, Represents an alkyl group or an aryl group.
- R 21 to R 24 are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group or aryl. Represents a group.
- Two of R 21 to R 24 may be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
- R 21 to R 24 are preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R 21 to R 24 are bonded to each other to form an aryl group is also preferred. Of these, an embodiment in which R 21 to R 24 are all hydrogen atoms is preferred. Any of the above-described substituents may further have a substituent.
- the compound represented by the formula (OS-101) is more preferably a compound represented by the formula (OS-102).
- the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
- Specific examples of the compound represented by the formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP2011-209692A, the contents of which are incorporated herein.
- b-9, b-16, b-31 and b-33 are preferable.
- Examples of commercially available products include WPAG-336 (manufactured by Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. it can.
- the photoacid generator sensitive to actinic rays those which do not contain a 1,2-quinonediazide compound are preferred.
- the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is 1 or less and is less sensitive than the oxime sulfonate compound.
- the oxime sulfonate compound acts as a catalyst for the deprotection of an acid group protected in response to an actinic ray, so that a large number of acids generated by the action of one photon are present.
- the oxime sulfonate compound has a broad ⁇ -conjugated system, it has absorption up to the long wavelength side, and not only deep ultraviolet rays (DUV), ArF rays, KrF rays, i rays, It shows very high sensitivity even in the g-line.
- DUV deep ultraviolet rays
- an acid-decomposability equivalent to or higher than that of an acetal or ketal can be obtained.
- an acid-decomposable group can be consumed reliably in a shorter post-bake.
- the oxime sulfonate compound that is a photoacid generator in combination, the sulfonic acid generation rate is increased, so that the generation of acid is accelerated and the decomposition of the acid-decomposable group of the resin is accelerated.
- the photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, based on the total solid content of the photosensitive resin composition. It is further preferable to use 10% by mass, more preferably 0.5 to 3% by mass, and still more preferably 0.5 to 1.2% by mass.
- a photo-acid generator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the photosensitive resin composition can contain other components.
- an organic solvent is preferably contained from the viewpoint of coatability.
- the photosensitive resin composition preferably contains an organic solvent, and may be prepared as a solution in which an optional component of a photoacid generator and various additives in addition to an acid-reactive resin is dissolved in an organic solvent. preferable.
- known organic solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether.
- Propylene glycol dialkyl ethers Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetate , Esters, ketones, amides, lactones and the like.
- organic solvent examples include (1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; (2) ethylene glycol dimethyl ether, ethylene glycol diethyl Ethylene glycol dialkyl ethers such as ether and ethylene glycol dipropyl ether; (3) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate Acetates; (4) propylene glycol Propylene glycol monoalkyl ethers such as monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; (5) Propylene glycol dialkyl
- these organic solvents may further contain benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-octanol, if necessary.
- Organic solvents such as nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate can also be added.
- the organic solvents described above propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, or a combination of both are preferred, and diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, or a combination of both are particularly preferred.
- These organic solvents can be used individually by 1 type or in mixture of 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the photosensitive resin composition preferably contains a basic compound, and from the viewpoint of applicability, it preferably contains a surfactant.
- the photosensitive resin composition contains a basic compound.
- the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Examples of aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
- Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
- Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, cyclohexylmorpholinoethylthiourea, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3
- Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
- Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
- the content of the basic compound is preferably 0.001 to 1 part by mass, preferably 0.002 to 1 part by mass with respect to 100 parts by mass of the acid-reactive resin. More preferably, it is 0.5 parts by mass.
- the basic compound may be used singly or in combination of two or more, preferably in combination of two or more, more preferably in combination of two, heterocyclic amine More preferably, two of these are used in combination. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the photosensitive resin composition contains a surfactant.
- a surfactant any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
- nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based and silicone surfactants. .
- fluorosurfactants and silicone surfactants examples include, for example, JP-A-62-036663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950. JP, 03-03540, JP 07-230165, JP 08-062834, 09-054432, 09-005988, 2001-330953.
- the surfactants described in each of the publications can be mentioned, and commercially available surfactants can also be used.
- Examples of commercially available surfactants that can be used include EFTOP EF301, EF303 (above, Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (above, made by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176. , F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PF-6320, etc.
- Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.
- a surfactant it contains a structural unit A and a structural unit B represented by the following formula (41), and is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
- a preferred example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.
- R 41 and R 43 each independently represent a hydrogen atom or a methyl group
- R 42 represents a linear alkylene group having 1 to 4 carbon atoms
- R 44 represents a hydrogen atom or 1 to 4 carbon atoms.
- L 4 represents an alkyl group
- L 4 represents an alkylene group having 3 to 6 carbon atoms
- p4 and q4 is the mass percentage representing the polymerization ratio
- p4 represents the following numbers 80 wt% to 10 wt%
- q4 represents a numerical value of 20% by mass to 90% by mass
- r4 represents an integer of 1 to 18
- n4 represents an integer of 1 to 10.
- L 4 is preferably a branched alkylene group represented by the following formula (42).
- R 45 in the formula (42) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of wettability with respect to the coated surface, and an alkyl group having 2 or 3 carbon atoms.
- the weight average molecular weight of the copolymer is more preferably 1,500 or more and 5,000 or less.
- the addition amount of the surfactant is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the acid-reactive resin. More preferably, the content is 0.01 to 1 part by mass.
- Surfactant can be used individually by 1 type or in mixture of 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the photosensitive resin composition usually inevitably contains a trace amount of metal impurities.
- metal impurities for example, salts of alkali metals or alkaline earth metals such as sodium, potassium, calcium and the like can be mentioned. It is presumed that an inorganic defect occurs due to the influence of this metal impurity (especially sodium, potassium, calcium).
- the total content of sodium ion, potassium ion and calcium ion in the photosensitive resin composition is, for example, in the range of 1 mass ppt to 1000 mass ppb, and further in the range of 50 mass ppt to 500 mass ppb. It is understood that it exists.
- the metal impurities are gently dispersed in the system by containing appropriate moisture, thereby preventing the aggregation of metal impurities and thereby suppressing the generation of inorganic defects. Is done.
- the amount of metal ions is measured by the method described in Examples described later.
- the static contact angle on the polyvinyl alcohol (PVA) film is preferably 60 ° or less, more preferably 50 ° or less, and further preferably 40 ° or less.
- the lower limit is practically 2 ° or more, more practically 5 ° or more, and more practically 10 ° or more.
- the photosensitive resin composition may be combined with a water-soluble resin composition containing a water-soluble resin to form a kit for forming a photosensitive layer and a water-soluble resin layer in this order. Furthermore, it is preferably used as a kit for processing an organic semiconductor layer. At this time, it is preferable to apply each component of the photosensitive resin composition and each component of the water-soluble resin composition described above as specific embodiments. In this invention, it is good also as a kit which combined the composition for organic-semiconductor formation further. As a specific aspect of the composition, it is preferable to apply the above-described organic semiconductor and each component of the composition.
- Patterning methods that can be suitably employed in the present invention include the following forms.
- processing (patterning) of the organic semiconductor layer will be described as an example, but it can also be used for patterning of layers other than the organic semiconductor layer.
- the patterning method of the organic semiconductor layer of this embodiment is (1) forming a water-soluble resin layer on the organic semiconductor layer; (2) forming a photosensitive layer on the side of the water-soluble resin layer opposite to the organic semiconductor layer; (3) a step of exposing the photosensitive layer; (4) a step of developing using a developer containing an organic solvent to produce a mask pattern; (5) a step of removing at least the non-masked water-soluble resin layer and the organic semiconductor layer by dry etching treatment; (6) a step of removing the water-soluble resin layer; including.
- the patterning method of the organic semiconductor layer of this embodiment includes a step of forming a water-soluble resin layer on the organic semiconductor layer. Usually, this process is performed after forming an organic semiconductor layer on a substrate. In this case, the water-soluble resin layer is formed on the surface opposite to the surface of the organic semiconductor on the substrate side.
- the water-soluble resin layer is usually provided on the surface of the organic semiconductor layer, but other layers may be provided without departing from the spirit of the present invention. Specific examples include a water-soluble undercoat layer. Further, only one water-soluble resin layer may be provided, or two or more layers may be provided. As described above, the water-soluble resin layer is preferably formed using a water-soluble resin composition.
- a photosensitive layer is formed using a photosensitive resin composition on the side opposite to the surface of the water-soluble resin layer on the organic semiconductor layer side.
- the photosensitive layer is preferably formed using a photosensitive resin composition, and more preferably formed using a chemically amplified photosensitive resin composition containing an acid-reactive resin and a photoacid generator. Is done.
- the chemically amplified photosensitive resin composition contains a photoacid generator. When exposed to light, an acid is generated, and the acid-reactive resin contained in the resist reacts to enable patterning and functions as a photosensitive layer.
- the solid content concentration of the photosensitive resin composition is usually 1.0 to 40% by mass, preferably 10 to 35% by mass, and more preferably 16 to 28% by mass. By setting the solid content concentration in the above range, the photosensitive resin composition can be uniformly applied on the water-soluble resin layer, and further, a resist pattern having a high resolution and a rectangular profile can be formed. It becomes possible.
- the solid content concentration is a percentage of the mass of other resist components excluding the organic solvent with respect to the total mass of the photosensitive resin composition.
- Step of exposing photosensitive layer >> (2) After forming the photosensitive layer in the step, the photosensitive layer is exposed. Specifically, the photosensitive layer is irradiated with actinic rays through a mask having a predetermined pattern. Exposure may be performed only once or multiple times. Specifically, actinic rays are irradiated in a predetermined pattern onto a substrate provided with a dry coating film of the photosensitive resin composition. Exposure may be performed through a mask, or a predetermined pattern may be drawn directly.
- an actinic ray having a wavelength of preferably 180 nm or more and 450 nm or less, more preferably 365 nm (i line), 248 nm (KrF line) or 193 nm (ArF line) can be used.
- a post-exposure heating step PEB
- a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, a light emitting diode (LED) light source, or the like can be used.
- actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used.
- i-line because the effect is suitably exhibited.
- wavelengths of 343 nm and 355 nm are preferably used for a solid (YAG) laser, and 193 nm (ArF line), 248 nm (KrF line), and 351 nm (Xe line) are preferably used for an excimer laser.
- 375 nm and 405 nm are preferably used in the semiconductor laser.
- the laser can be applied to the photosensitive layer in one or more times.
- the exposure amount is preferably 40 to 120 mJ, and more preferably 60 to 100 mJ.
- the energy density per pulse of the laser is preferably 0.1 mJ / cm 2 or more and 10,000 mJ / cm 2 or less.
- 0.3 mJ / cm 2 or more is more preferable, and 0.5 mJ / cm 2 or more is more preferable.
- more preferably 1,000 mJ / cm 2 or less, 100 mJ / cm 2 or less is more preferred.
- the pulse width is preferably 0.1 nanosecond (hereinafter referred to as “nsec”) or more and 30,000 nsec or less.
- nsec nanosecond
- 0.5 nsec or more is more preferable, and 1 nsec or more is more preferable.
- 1,000 nsec or less is more preferable, and 50 nsec or less is further preferable.
- the frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less, and more preferably 10 Hz or more and 1,000 Hz or less.
- the frequency of the laser is more preferably 10 Hz or more, further preferably 100 Hz or more.
- the laser is preferable in that it can be easily focused as compared with a mercury lamp, and a mask for forming a pattern in the exposure process is unnecessary and the cost can be reduced.
- the exposure apparatus There are no particular restrictions on the exposure apparatus, but commercially available devices include Calisto (buoy technology), AEGIS (buoy technology), DF2200G (Dainippon Screen Mfg. Co., Ltd.). Etc.) can be used. Further, devices other than those described above are also preferably used. If necessary, the amount of irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.
- a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.
- Step (3) the photosensitive layer is exposed through a mask and then developed using a developer containing an organic solvent (hereinafter also referred to as an organic developer). Development is preferably a negative type. Sp value of the solvent contained in the developer is preferably less than 19 MPa 1/2, and more preferably 18 MPa 1/2 or less.
- organic solvent contained in the developer polar solvents such as ketone solvents, ester solvents, amide solvents, and hydrocarbon solvents can be used.
- Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, Examples include methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
- ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl.
- amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, and the like. Can be used.
- hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
- the organic solvent may be used alone or in combination of two or more. Moreover, you may mix and use with organic solvents other than the above.
- the water content of the whole developer is preferably less than 10% by mass, and more preferably substantially free of moisture.
- substantially as used herein means, for example, that the water content of the entire developing solution is 3% by mass or less, and more preferably the measurement limit or less.
- the amount of the organic solvent used relative to the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developer.
- the organic developer preferably contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, and amide solvents.
- the organic developer may contain an appropriate amount of a basic compound as required. Examples of the basic compound include those described in the above basic compound section.
- the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and further preferably 2 kPa or less at 20 ° C.
- the solvent having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone and diisobutyl.
- Ketone solvents such as ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylisobutylketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol Monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, Ester solvents such as butyl acid, propyl formate, ethyl lactate, butyl lactate, propyl lactate, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, xy
- the solvent having a vapor pressure of 2 kPa or less which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, Ketone solvents such as methylcyclohexanone and phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, Ester solvents such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, N-methyl-2- Pyrrolidone,
- an appropriate amount of one or more surfactants can be added to the developer as required. Although it does not specifically limit as surfactant, for example, surfactant described in the item of said water-soluble resin composition is used preferably.
- the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0, based on the total amount of the developer. 0.01 to 0.5% by mass.
- a development method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
- dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
- paddle a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time
- spray method a method of spraying the developer on the substrate surface
- the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is , Preferably 2 mL / sec / mm 2 or less, more preferably 1.5 mL / sec / mm 2 or less, and even more preferably 1 mL / sec / mm 2 or less.
- the flow rate Preferably 2 mL / sec / mm 2 or less, more preferably 1.5 mL / sec / mm 2 or less, and even more preferably 1 mL / sec / mm 2 or less.
- There is no particular lower limit of the flow rate but 0.2 mL / second / mm 2 or more is preferable in consideration of throughput.
- the details of this mechanism are not clear, but perhaps by setting the discharge pressure in the above range, the pressure applied to the photosensitive layer by the developer is reduced, and the resist pattern on the photosensitive layer is inadvertently scraped or broken. This is considered to be suppressed.
- the developer discharge pressure (mL / second / mm 2 ) is a value at the developing nozzle outlet in the developing device.
- Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
- Step of removing at least the non-masked water-soluble resin layer and the organic semiconductor layer by dry etching treatment At least the water-soluble resin layer and the organic semiconductor layer in the non-mask portion are removed by an etching process.
- the non-mask portion represents a portion where the photosensitive layer has been removed in the development process.
- at least the water-soluble resin layer and the organic semiconductor layer are dry etched using the resist pattern as an etching mask.
- Representative examples of dry etching include Japanese Patent Application Laid-Open Nos. 59-126506, 59-046628, 58-009108, 58-002809, and 57-148706.
- the dry etching is preferably performed in the following manner from the viewpoint of forming the pattern cross section closer to a rectangle and reducing damage to the organic semiconductor layer.
- a second stage etching is performed in which a mixed gas of (N 2 ) and oxygen gas (O 2 ) is used, and etching is preferably performed to the vicinity of the region (depth) where the organic semiconductor layer is exposed, and after the organic semiconductor layer is exposed
- a form including overetching to be performed is preferable.
- Dry etching is performed by obtaining etching conditions in advance by the following method.
- the etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated.
- the time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated.
- the first stage etching is performed according to the etching time calculated in (2) above.
- the second stage etching is performed according to the etching time calculated in (2) above.
- the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time.
- Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.
- the mixed gas used in the first stage etching step preferably contains a fluorine-based gas and an oxygen gas (O 2 ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape.
- the organic semiconductor layer can be prevented from being damaged by etching the region where the organic semiconductor layer is not exposed.
- the second-stage etching process and the over-etching process may be performed by performing etching to a region where the organic semiconductor layer is not exposed by a mixed gas of fluorine-based gas and oxygen gas in the first-stage etching process. From the viewpoint of avoiding damage, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas. It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is.
- the latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable.
- the etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.
- Etching preferably includes an over-etching process.
- the overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first.
- the over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.
- Step of removing water-soluble resin layer >> After the etching, it is preferable to remove the water-soluble resin layer using a solvent (usually water).
- a solvent usually water
- the method for removing the water-soluble resin layer with water include a method for removing the water-soluble resin layer by spraying cleaning water onto the resist pattern from a spray type or shower type spray nozzle.
- the washing water pure water can be preferably used.
- the injection nozzle include an injection nozzle in which the entire substrate is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire substrate.
- the resist pattern is more effectively removed by spraying the cleaning water by moving from the center of the substrate to the end of the substrate at least twice during the process of removing the water-soluble resin layer. be able to. It is also preferable to perform a process such as drying after removing water.
- the drying temperature is preferably 80 to 120 ° C.
- the photosensitive layer of the present invention can be used for production of an electronic device using an organic semiconductor.
- an electronic device is a device that contains a semiconductor and has two or more electrodes, and a current flowing between the electrodes and a generated voltage are controlled by electricity, light, magnetism, chemical substances, or the like, or It is a device that generates light, electric field, magnetic field, etc. by applied voltage or current.
- Examples include organic photoelectric conversion elements, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, information recording elements, and the like.
- the organic photoelectric conversion element can be used for both optical sensor applications and energy conversion applications (solar cells).
- organic field effect transistors, organic photoelectric conversion elements, and organic electroluminescence elements are preferable as applications, more preferably organic field effect transistors and organic photoelectric conversion elements, and particularly preferably organic field effect transistors. .
- Mw weight average molecular weight
- a solution prepared by dissolving 6 mol% of methyl isobutyl ketone in 75.3 g of the total monomer amount was added dropwise over 6 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then poured into 720 ml of heptane / 80 ml of ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain 18.3 g of acid-reactive resin A-1.
- the obtained resin had a weight average molecular weight of 9,300 and a dispersity (Mw / Mn) of 1.98.
- the white powder produced by reprecipitation of the reaction solution in heptane was collected by filtration to obtain acid-reactive resin A-2.
- the weight average molecular weight (Mw) was 45,000.
- the amount of the component having Mw of 1,000 or less was 3% by mass.
- the amount of water in the composition was measured using the following Karl Fischer moisture meter after preparation. If necessary, a photosensitive resin composition was prepared by adding ultrapure water so that the amount of water in the composition was within the range described in the table. Details of each component are shown in Table 1.
- An organic semiconductor coating liquid (composition for forming an organic semiconductor) having the following composition was spin-coated on a circular glass substrate and dried at 130 ° C. for 10 minutes to form an organic semiconductor layer.
- the film thickness was 150 nm.
- a water-soluble resin composition was spin-coated on the surface of the organic semiconductor layer and dried at 100 ° C. for 1 minute to form a water-soluble resin layer having a thickness of 2.0 ⁇ m.
- a photosensitive resin composition was spin-coated on the surface of the water-soluble resin layer thus formed, and dried (prebaked) at 100 ° C. for 1 minute to form a photosensitive layer.
- the film thickness was 2.0 ⁇ m.
- PEB post-baking
- the acid generator By the exposure and development, the acid generator generates an acid by irradiation with i-line or KrF-ray, and the generation of the acid reduces the solubility in butyl acetate except for Example 6, and Example 6 is soluble in butyl acetate. It was confirmed that the speed increased.
- the moisture content in the photosensitive resin composition was measured by the following method. Using the Hiranuma automatic moisture analyzer AQV-2200, the moisture content in the composition weight was calculated.
- the total content of sodium ions, potassium ions and calcium ions in the photosensitive resin composition was measured by the following method.
- Na, K, and Ca were obtained by metal analysis using a high-frequency inductively coupled plasma mass spectrometer (ICP-MS-Inductively Coupled Plasma Mass Spectrometer: 7500 cs manufactured by Agilent Technologies).
- the obtained metal concentration value was divided by the polymer concentration to calculate the metal concentration (metal impurity content) in terms of polymer solid content.
- ⁇ Defects> A 13 mm square exposure area was exposed on an 8-inch wafer (1 inch is 2.54 cm), post-exposure baking (PEB) was performed, and organic solvent development was performed using butyl acetate. The number of defects in the opening of 13 mm square was confirmed by a defect inspection apparatus COMPLUS 3T (manufactured by AMAT), with a defect having a length of 5000 nm or more as a residue. Evaluation was performed by the average value of the measured values at 10 locations. Each of the organic defects and the inorganic defects was measured and evaluated.
- the shape of defect residues having characteristic nuclei was observed with SEM VISION G4 (manufactured by AMAT), and the presence or absence of metal components was analyzed by energy dispersive X-ray analysis (EDX).
- EDX energy dispersive X-ray analysis
- the residues those in which the metal component was detected were defined as metal residues, and the others were defined as organic residues.
- the organic residue means a defect on the surface of the cured film in which at least carbon atoms and oxygen atoms are detected but no metal component is detected.
- ⁇ Basic compound> C-1 is a thiourea derivative represented by the following formula
- Photosensitive resin composition using C-2 (N, N-dibutylaniline) instead of basic compound C-1 of Example 1, D-2 (PFNO from OMNOVA) instead of surfactant D-1 (Trade name)), a mixed solvent of E-1: E-2 (ethyl 3-ethoxypropionate) 70: 30 (mass ratio) was used instead of the solvent E-1.
- the photosensitive resin composition made into (mass ratio) was prepared, respectively.
- a laminate sample was prepared using each photosensitive resin composition. As a result of measuring the occurrence of defects for each sample, the result of “A” was obtained in the comprehensive evaluation for all the substrates.
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Abstract
Description
そこで、本発明は水溶性樹脂層の上側に積層させた感光層を露光・現像するに当たり、このときに生じるディフェクトを抑制ないし消失させることができる感光層、積層体、感光性樹脂組成物、キットおよび感光性樹脂組成物の製造方法を提供することを目的とする。 By the above-described technique, the protection of the organic semiconductor layer and the like can be ensured by interposing a water-soluble resin layer between the semiconductor layer such as the organic semiconductor layer and the photosensitive layer. The present inventors have made further improvements and focused on improving the production quality when the photosensitive layer is exposed and developed with respect to the photosensitive layer and the laminate including the photosensitive layer. Specifically, referring to FIG. 3, in this conventional example, a laminate in which an
Therefore, in the present invention, when exposing and developing the photosensitive layer laminated on the upper side of the water-soluble resin layer, a photosensitive layer, a laminate, a photosensitive resin composition, and a kit that can suppress or eliminate defects generated at this time. And it aims at providing the manufacturing method of the photosensitive resin composition.
<2>上記感光層がi線の照射に対して感光能を有する、<1>に記載の感光層。
<3>ポリビニルアルコール膜上における上記感光性樹脂組成物の静止接触角が2°以上60°以下である、<1>または<2>に記載の感光層。
<4>上記感光層における樹脂の酸の作用による溶解速度の変化が溶解速度の低下である、<1>~<3>のいずれか1つに記載の感光層。
<5>上記感光層における樹脂が下記式(1)で表される構成単位を有するポリマーを含む、<1>~<4>のいずれか1つに記載の感光層;
式中、R8は水素原子またはアルキル基を表し、L1はカルボニル基またはフェニレン基を表し、R1~R7はそれぞれ独立に水素原子またはアルキル基を表す。
<6>上記感光性樹脂組成物中のナトリウムイオン、カリウムイオンおよびカルシウムイオンの合計含有量が1質量ppt~1000質量ppbである、<1>~<5>のいずれか1つに記載の感光層。
<7>有機半導体層加工用である、<1>~<6>のいずれか1つに記載の感光層。
<8><1>~<7>のいずれか1つに記載の感光層と水溶性樹脂層とを有する積層体。
<9>さらに、有機半導体層を有し、上記有機半導体層、上記水溶性樹脂層、上記感光層の順に積層している、<8>に記載の積層体。
<10>感光層を形成するための感光性樹脂組成物であって、上記感光層は水溶性樹脂層と組み合わせて積層体をなす層であり、活性光線および放射線の少なくとも一方の照射により酸を発生する化合物と、酸の作用により酢酸ブチルに対する溶解速度が変化する樹脂と、水とを含み、上記感光性樹脂組成物中の水の含有量が0.008質量%以上1質量%以下である、感光性樹脂組成物。
<11>有機半導体層加工用である、<10>に記載の感光性樹脂組成物。
<12>水溶性樹脂層と感光層とをこの順に形成するためのキットであって、<10>または<11>に記載の感光性樹脂組成物と水溶性樹脂組成物とを有するキット。
<13>有機半導体層加工用である、<12>に記載のキット。
<14>活性光線および放射線の少なくとも一方の照射により酸を発生する化合物と、酸の作用により酢酸ブチルに対する溶解速度が変化する樹脂を含む組成物の水分量を調節することを含む、あるいは、
活性光線および放射線の少なくとも一方の照射により酸を発生する化合物と、酸の作用により酢酸ブチルに対する溶解速度が変化する樹脂を含む組成物に含まれる原料の水分量を調節することを含む、<10>または<11>に記載の感光性樹脂組成物の製造方法。 <1> A photosensitive layer included in a laminate having a water-soluble resin layer and a photosensitive layer, wherein the compound generates an acid upon irradiation with at least one of actinic rays and radiation, and a dissolution rate in butyl acetate by the action of the acid. Is a layer formed from a photosensitive resin composition containing a resin that changes in water and water, and the water content in the photosensitive resin composition is 0.008% by mass or more and 1% by mass or less. layer.
<2> The photosensitive layer according to <1>, wherein the photosensitive layer has photosensitivity to i-ray irradiation.
<3> The photosensitive layer according to <1> or <2>, wherein a static contact angle of the photosensitive resin composition on the polyvinyl alcohol film is 2 ° or more and 60 ° or less.
<4> The photosensitive layer according to any one of <1> to <3>, wherein the change in the dissolution rate due to the action of the acid of the resin in the photosensitive layer is a decrease in the dissolution rate.
<5> The photosensitive layer according to any one of <1> to <4>, wherein the resin in the photosensitive layer includes a polymer having a structural unit represented by the following formula (1);
In the formula, R 8 represents a hydrogen atom or an alkyl group, L 1 represents a carbonyl group or a phenylene group, and R 1 to R 7 each independently represents a hydrogen atom or an alkyl group.
<6> The photosensitive composition according to any one of <1> to <5>, wherein the total content of sodium ions, potassium ions, and calcium ions in the photosensitive resin composition is 1 mass ppt to 1000 mass ppb. layer.
<7> The photosensitive layer according to any one of <1> to <6>, which is used for processing an organic semiconductor layer.
<8> A laminate having the photosensitive layer according to any one of <1> to <7> and a water-soluble resin layer.
<9> The laminate according to <8>, further including an organic semiconductor layer, wherein the organic semiconductor layer, the water-soluble resin layer, and the photosensitive layer are laminated in this order.
<10> A photosensitive resin composition for forming a photosensitive layer, wherein the photosensitive layer is a layer that is combined with a water-soluble resin layer to form a laminate, and an acid is irradiated by irradiation with at least one of actinic rays and radiation. The generated compound, a resin whose dissolution rate in butyl acetate is changed by the action of an acid, and water, and the water content in the photosensitive resin composition is 0.008% by mass or more and 1% by mass or less. , Photosensitive resin composition.
<11> The photosensitive resin composition according to <10>, which is used for processing an organic semiconductor layer.
<12> A kit for forming a water-soluble resin layer and a photosensitive layer in this order, comprising the photosensitive resin composition according to <10> or <11> and the water-soluble resin composition.
<13> The kit according to <12>, which is for processing an organic semiconductor layer.
<14> adjusting the water content of a composition comprising a compound that generates an acid upon irradiation with at least one of actinic rays and radiation, and a resin whose dissolution rate in butyl acetate is changed by the action of the acid, or
Adjusting the water content of the raw material contained in the composition comprising a compound that generates an acid upon irradiation with at least one of actinic rays and radiation, and a resin that changes the dissolution rate in butyl acetate by the action of the acid, <10 > Or <11> The method for producing a photosensitive resin composition according to <11>.
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
また、本明細書における「活性光線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等を意味する。また、本発明において光とは、活性光線または放射線を意味する。本明細書における「露光」とは、特に断らない限り、水銀灯、エキシマレーザに代表される遠紫外線、X線、EUV光などによる露光のみならず、電子線、イオンビーム等の粒子線による描画も含む。
本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
また、本明細書において、“(メタ)アクリレート”はアクリレートおよびメタクリレートの双方、または、いずれかを表し、“(メタ)アクリル”はアクリルおよびメタクリルの双方、または、いずれかを表し、“(メタ)アクリロイル”はアクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
本明細書において「工程」との語は、独立した工程を意味するだけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、その工程は本用語に含まれる。
本明細書において固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量の百分率である。
本明細書において、「上」「下」と記載したときには、その構造の上側または下側であればよい。すなわち、他の構造を介在していてもよく、接している必要はない。なお、特に断らない限り、感光層側を上とし基板ないし有機半導体層側を下と称する。 The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “active light” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. In this specification, “exposure” means not only exposure by far ultraviolet rays, X-rays, EUV light typified by mercury lamps and excimer lasers, but also drawing by particle beams such as electron beams and ion beams, unless otherwise specified. Including.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In this specification, the term “process” not only means an independent process, but if the intended action of the process is achieved even if it cannot be clearly distinguished from other processes, the process Is included in this term.
In this specification, solid content concentration is the percentage of the mass of the other components excluding the solvent with respect to the total mass of the composition.
In this specification, when “upper” and “lower” are described, they may be above or below the structure. That is, other structures may be interposed and do not need to be in contact with each other. Unless otherwise specified, the photosensitive layer side is referred to as the upper side, and the substrate or organic semiconductor layer side is referred to as the lower side.
感光性樹脂組成物の含水量を上記上限値以下とすることにより、インターミクス(層間の混合)を抑制してディフェクトを抑制することができる。一方、含水量を上記下限値以上にすることにより、金属不純物に起因するディフェクトを効果的に抑制しうるものと考えられる。
すなわち、水分量が多すぎると、感光性樹脂組成物が水溶性樹脂層と層間(界面)で混合して有機成分のディフェクト(有機系ディフェクト)を発生しやすくなってしまう。しかしながら、本発明においては、水を完全に排除してしまうのではなく、感光性樹脂組成物の含水量を適量とした。これにより、溶剤などの原料に含まれる、完全には排除できていない金属不純物(無機系ディフェクト)を水が穏やかに溶解または分散させ、さらに金属不純物が溶解または分散した水を溶剤が包含して、感光性樹脂組成物層全体に分散させるものと考えられる。結果として、金属不純物等に起因する無機成分のディフェクトの発生を抑制することができる。つまり、金属不純物等がコアとなりディフェクトの原因になるが、これを水の作用で感光性樹脂組成物中に穏やかに分散させることによって、ディフェクトを抑制ないし消失させることができたものと推定される。 The photosensitive layer of the present invention is a photosensitive layer contained in a laminate having a water-soluble resin layer and a photosensitive layer, and is a compound that generates an acid upon irradiation with at least one of actinic rays and radiation (this compound is referred to herein). Is a layer formed from a photosensitive resin composition containing a resin (acid-reactive resin) whose dissolution rate in butyl acetate is changed by the action of an acid, and water. The water content in the photosensitive resin composition is 0.008% by mass or more and 1% by mass or less. As a result, defects on the water-soluble resin layer could be effectively suppressed or eliminated. The reason is estimated as follows.
By setting the water content of the photosensitive resin composition to the upper limit value or less, intermix (mixing between layers) can be suppressed and defects can be suppressed. On the other hand, it is considered that defects caused by metal impurities can be effectively suppressed by setting the water content to the lower limit value or more.
That is, if the amount of water is too large, the photosensitive resin composition is likely to mix with the water-soluble resin layer and the interlayer (interface) to easily cause organic component defects (organic defects). However, in the present invention, water is not completely eliminated, but the water content of the photosensitive resin composition is set to an appropriate amount. As a result, water gently dissolves or disperses the metal impurities (inorganic defects) contained in the raw material such as the solvent, and the solvent includes the water in which the metal impurities are dissolved or dispersed. It is considered that it is dispersed throughout the photosensitive resin composition layer. As a result, it is possible to suppress the occurrence of inorganic component defects caused by metal impurities and the like. In other words, metal impurities and the like become cores and cause defects, but it is estimated that the defects could be suppressed or eliminated by gently dispersing them in the photosensitive resin composition by the action of water. .
図1では、有機半導体層の上に設ける形態を例に示したが、他の材料の表面に水溶性樹脂層と感光層を組み合わせて用いてもよい。本発明では、有機半導体層加工用であることが好ましい。
本発明の積層体は、本発明の感光層と水溶性樹脂層とを有する積層体であり、好ましくは、さらに、有機半導体層を有し、上記有機半導体層、上記水溶性樹脂層、上記感光層の順に積層している積層体である。そして、これらの層は互いに接していることが好ましい。
以下、各層の特徴およびこれを構成する材料等について説明する。 The photosensitive layer of the present invention is preferably used in combination with a water-soluble resin layer and disposed in contact with both. In an embodiment of the present invention, an
In FIG. 1, the form provided on the organic semiconductor layer is shown as an example. However, a water-soluble resin layer and a photosensitive layer may be used in combination on the surface of another material. In the present invention, the organic semiconductor layer is preferably used for processing.
The laminate of the present invention is a laminate having the photosensitive layer of the present invention and a water-soluble resin layer, and preferably further includes an organic semiconductor layer, the organic semiconductor layer, the water-soluble resin layer, and the photosensitive layer. It is the laminated body laminated | stacked in order of the layer. These layers are preferably in contact with each other.
Hereinafter, features of each layer and materials constituting the layer will be described.
有機半導体層は、半導体の特性を示す有機材料を含む層である。有機半導体には、無機材料からなる半導体の場合と同様に、正孔をキャリアとして伝導するp型有機半導体と、電子をキャリアとして伝導するn型有機半導体がある。有機半導体層中のキャリアの流れやすさはキャリア移動度μで表される。用途にもよるが、一般に移動度は高い方がよく、10-7cm2/Vs以上であることが好ましく、10-6cm2/Vs以上であることがより好ましく、10-5cm2/Vs以上であることがさらに好ましい。移動度は電界効果トランジスタ(FET)素子を作製したときの特性や飛行時間計測(TOF)法により求めることができる。 <Organic semiconductor layer>
The organic semiconductor layer is a layer containing an organic material exhibiting semiconductor characteristics. As in the case of a semiconductor made of an inorganic material, there are a p-type organic semiconductor that conducts holes as carriers and an n-type organic semiconductor that conducts electrons as carriers. The ease of carrier flow in the organic semiconductor layer is represented by carrier mobility μ. Although it depends on the application, in general, the mobility should be higher, preferably 10 −7 cm 2 / Vs or more, more preferably 10 −6 cm 2 / Vs or more, more preferably 10 −5 cm 2 / Vs. More preferably, it is Vs or higher. The mobility can be obtained by characteristics when a field effect transistor (FET) element is manufactured or by a time-of-flight measurement (TOF) method.
溶剤としては、例えば、ヘキサン、オクタン、デカン、トルエン、キシレン、エチルベンゼン、1-メチルナフタレン等の炭化水素系溶剤;例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤;例えば、ジクロロメタン、クロロホルム、テトラクロロメタン、ジクロロエタン、トリクロロエタン、テトラクロロエタン、クロロベンゼン、ジクロロベンゼン、クロロトルエン等のハロゲン化炭化水素系溶剤;例えば、酢酸エチル、酢酸ブチル、酢酸アミル等のエステル系溶剤;例えば、メタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、メチルセロソルブ、エチルセロソルブ、エチレングリコール等のアルコール系溶剤;例えば、ジブチルエーテル、テトラヒドロフラン、ジオキサン、アニソール等のエーテル系溶剤;例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、1-メチル-2-ピロリドン、1-メチル-2-イミダゾリジノン、ジメチルスルフォキサイド等の極性溶剤などが挙げられる。これらの溶剤は1種のみを用いてもよいし、2種以上を用いてもよい。
有機半導体層を形成する組成物(有機半導体形成用組成物)における有機半導体の割合は、好ましくは0.1~80質量%、より好ましくは0.1~30質量%であり、これにより任意の厚さの膜を形成できる。 The above materials are usually blended in a solvent, applied in layers on a substrate, dried and formed into a film. As an application method, description of a water-soluble resin layer described later can be referred to.
Examples of the solvent include hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, and 1-methylnaphthalene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Halogenated hydrocarbon solvents such as chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene; for example, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate; for example, methanol, propanol Alcohol solvents such as butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol; Ether solvents such as tetrahydrofuran, dioxane and anisole; for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, dimethylsulfoxide Examples include polar solvents such as side. These solvent may use only 1 type and may use 2 or more types.
The ratio of the organic semiconductor in the composition for forming the organic semiconductor layer (composition for forming an organic semiconductor) is preferably 0.1 to 80% by mass, more preferably 0.1 to 30% by mass. A film having a thickness can be formed.
用途によっては単独および種々の半導体材料や添加剤を添加した混合溶液を基板等の上に塗布し、複数の材料種からなるブレンド膜としてもよい。例えば、光電変換層を作製する場合、別の半導体材料との混合溶液を用いることなどができる。
また、製膜の際、基板を加熱または冷却してもよく、基板の温度を変化させることで膜質や膜中での分子のパッキングを制御することが可能である。基板の温度としては特に制限はないが、好ましくは-200℃~400℃、より好ましくは-100℃~300℃、さらに好ましくは0℃~200℃である。
形成された有機半導体層は、後処理により特性を調整することができる。例えば、加熱処理や蒸気化した溶剤を暴露することにより膜のモルホロジーや膜中での分子のパッキングを変化させることで特性を向上させることが可能である。また、酸化性または還元性のガスや溶剤、物質などにさらす、あるいはこれらを混合することで酸化あるいは還元反応を起こし、膜中でのキャリア密度を調整することができる。
有機半導体層の膜厚は、特に制限されず、用いられる電子デバイスの種類などにより異なるが、好ましくは5nm~50μm、より好ましくは10nm~5μm、さらに好ましくは20nm~500nmである。 When the resin binder is blended, the blending amount is preferably 0.1 to 30% by mass in the organic semiconductor layer. Only one type of resin binder may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
Depending on the application, a single layer or a mixed solution to which various semiconductor materials and additives are added may be applied onto a substrate or the like to form a blend film composed of a plurality of material types. For example, when a photoelectric conversion layer is manufactured, a mixed solution with another semiconductor material can be used.
In film formation, the substrate may be heated or cooled, and the film quality and packing of molecules in the film can be controlled by changing the temperature of the substrate. The temperature of the substrate is not particularly limited, but is preferably −200 ° C. to 400 ° C., more preferably −100 ° C. to 300 ° C., and further preferably 0 ° C. to 200 ° C.
The characteristics of the formed organic semiconductor layer can be adjusted by post-processing. For example, it is possible to improve the characteristics by changing the film morphology and the molecular packing in the film by exposing to a heat treatment or a vaporized solvent. Further, by exposing to an oxidizing or reducing gas, solvent, substance, or the like, or mixing them, an oxidation or reduction reaction can be caused to adjust the carrier density in the film.
The thickness of the organic semiconductor layer is not particularly limited and varies depending on the type of electronic device used, but is preferably 5 nm to 50 μm, more preferably 10 nm to 5 μm, and still more preferably 20 nm to 500 nm.
水溶性樹脂層は水溶性樹脂を含み、水溶性樹脂組成物から形成されることが好ましい。水溶性樹脂とは、20℃における水100gに対する溶解した樹脂の量が1g以上である樹脂をいい、5g以上である樹脂が好ましく、10g以上であることがより好ましく、30g以上であることがさらに好ましい。上限はないが、20gであることが実際的である。 <Water-soluble resin layer (water-soluble resin composition)>
The water-soluble resin layer preferably contains a water-soluble resin and is formed from a water-soluble resin composition. The water-soluble resin refers to a resin in which the amount of dissolved resin with respect to 100 g of water at 20 ° C. is 1 g or more, preferably 5 g or more, more preferably 10 g or more, and further preferably 30 g or more. preferable. There is no upper limit, but it is practical to be 20 g.
また、本発明で用いる水溶性樹脂(上記PVP、PVA)の分散度(重量平均分子量/数平均分子量)は、1.0~5.0が好ましく、2.0~4.0がより好ましい。 The weight average molecular weight of the water-soluble resin is not particularly limited, but the weight average molecular weight of the polyvinylpyrrolidone used in the present invention is preferably 50,000 to 400,000. The weight average molecular weight of the polyvinyl alcohol used in the present invention is preferably 15,000 to 100,000. For other resins, it is preferably in the range of 10,000 to 300,000.
Further, the dispersity (weight average molecular weight / number average molecular weight) of the water-soluble resin (PVP, PVA) used in the present invention is preferably 1.0 to 5.0, more preferably 2.0 to 4.0.
水溶性樹脂層は、例えば、1種または2種以上の上記水溶性樹脂を含む水溶性樹脂組成物を有機半導体層の上に適用し、乾燥させることよって形成することができる。通常は、水溶性樹脂組成物は、溶剤として水を含み、さらに他の添加剤を含んでいてもよい。
水溶性樹脂組成物の固形分濃度は、0.5~30質量%であることが好ましく、1.0~20質量%であることがより好ましく、2.0~14質量%であることがさらに好ましい。固形分濃度を上記範囲とすることでより均一に塗布することができる。 The thickness of the water-soluble resin layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1.0 μm or more, and further preferably 2.0 μm or more. As an upper limit of the thickness of a water-soluble resin layer, 10 micrometers or less are preferable, 5.0 micrometers or less are more preferable, and 3.0 micrometers or less are further more preferable.
The water-soluble resin layer can be formed, for example, by applying a water-soluble resin composition containing one or more of the above water-soluble resins on the organic semiconductor layer and drying it. Usually, the water-soluble resin composition contains water as a solvent and may further contain other additives.
The solid content concentration of the water-soluble resin composition is preferably 0.5 to 30% by mass, more preferably 1.0 to 20% by mass, and further preferably 2.0 to 14% by mass. preferable. It can apply | coat more uniformly by making solid content concentration into the said range.
界面活性剤としては、表面張力を低下させるものであれば、ノニオン系、アニオン系、両性フッ素系など、どのようなものでもかまわない。界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレンステアレート等のポリオキシエチレンアルキルエステル類、ソルビタンモノラウレート、ソルビタンモノステアレート、ソルビタンジステアレート、ソルビタンモノオレエート、ソルビタンセスキオレエート、ソルビタントリオレエート等のソルビタンアルキルエステル類、グリセロールモノステアレート、グリセロールモノオレエート等のモノグリセリドアルキルエステル類等、フッ素あるいはケイ素を含有するオリゴマー等、アセチレングリコール、アセチレングリコールのエチレンオキシド付加物等の、ノニオン系界面活性剤;ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩類、ブチルナフタレンスルホン酸ナトリウム、ペンチルナフタレンスルホン酸ナトリウム、ヘキシルナフタレンスルホン酸ナトリウム、オクチルナフタレンスルホン酸ナトリウム等のアルキルナフタレンスルホン酸塩類、ラウリル硫酸ナトリウム等のアルキル硫酸塩類、ドデシルスルホン酸ナトリウム等のアルキルスルホン酸塩類、ジラウリルスルホコハク酸ナトリウム等のスルホコハク酸エステル塩類等の、アニオン系界面活性剤;ラウリルベタイン、ステアリルベタイン等のアルキルベタイン類、アミノ酸類等の、両性界面活性剤が使用可能である。 The water-soluble resin composition preferably further contains a surfactant for improving coatability.
As the surfactant, any surfactant such as nonionic, anionic, and amphoteric fluorine may be used as long as it reduces the surface tension. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and other polyoxyethylene alkyl ethers. Oxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters such as polyoxyethylene stearate, sorbitan monolaurate, sorbitan monostearate, sorbitan distearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, etc. Sorbitan alkyl esters, monoglyceride alkyl esters such as glycerol monostearate and glycerol monooleate Nonionic surfactants such as oligomers containing fluorine or silicon, acetylene glycol, ethylene oxide adducts of acetylene glycol, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, sodium butyl naphthalene sulfonate, pentyl naphthalene sulfonic acid Alkyl naphthalene sulfonates such as sodium, sodium hexyl naphthalene sulfonate, sodium octyl naphthalene sulfonate, alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates such as sodium dodecyl sulfonate, sulfosuccinic acid such as sodium dilauryl sulfosuccinate Anionic surfactants such as ester salts; alkylbetaines such as lauryl betaine and stearyl betaine, amino Classes such as the amphoteric surfactant can be used.
本発明の感光層は、酸発生剤と、酸反応性樹脂と、水とを含む感光性樹脂組成物から形成される層である。
本発明における感光層においては、これを形成する感光性樹脂組成物が水を含んでいる。感光性樹脂組成物に含まれる水の量は0.008質量%以上と規定され、0.009質量%以上が好ましく、0.01質量%以上がより好ましい。上限は1質量%以下に規制され、0.8質量%以下が好ましく、0.7質量%以下がより好ましく、0.05質量%以下であってもよい。上述のとおり、この水分量が多すぎると感光層の現像により水溶性樹脂層表面へのディフェクトの発生が顕著となる。一方、水を完全に排除してしまうと、かえってディフェクトの発生を抑えることができない。したがって、本発明では、水を少量でかつ適量を感光性樹脂組成物に含ませ、ディフェクトの発生を抑制ないし消失させることに成功した。
感光性樹脂組成物における水分量の調節は常法によればよい。例えば、酸発生剤と、酸反応性樹脂を含む組成物の水分量を調節することを含む、あるいは、酸発生剤と酸反応性樹脂を含む組成物に含まれる原料の水分量を調節することを含む、感光性樹脂組成物の製造方法が挙げられる。 <Photosensitive layer (photosensitive resin composition)>
The photosensitive layer of the present invention is a layer formed from a photosensitive resin composition containing an acid generator, an acid-reactive resin, and water.
In the photosensitive layer in the present invention, the photosensitive resin composition forming the photosensitive layer contains water. The amount of water contained in the photosensitive resin composition is defined as 0.008% by mass or more, preferably 0.009% by mass or more, and more preferably 0.01% by mass or more. The upper limit is regulated to 1% by mass or less, preferably 0.8% by mass or less, more preferably 0.7% by mass or less, and may be 0.05% by mass or less. As described above, when the amount of water is too large, the occurrence of defects on the surface of the water-soluble resin layer becomes remarkable due to the development of the photosensitive layer. On the other hand, if water is completely eliminated, the occurrence of defects cannot be suppressed. Therefore, in the present invention, a small amount of water and an appropriate amount are included in the photosensitive resin composition, and the generation of defects has been suppressed or eliminated.
Adjustment of the water content in the photosensitive resin composition may be carried out by a conventional method. For example, adjusting the water content of a composition containing an acid generator and an acid-reactive resin, or adjusting the water content of a raw material contained in a composition containing an acid generator and an acid-reactive resin The manufacturing method of the photosensitive resin composition containing this is mentioned.
また、酸反応性樹脂に含まれる重量平均分子量1,000以下の成分の量が、全酸反応性樹脂成分の10質量%以下であることが好ましく、5質量%以下であることがより好ましい。このような構成とすることにより、樹脂製造ロット間の感度変動をより効果的に低減することができる。
酸反応性樹脂の分散度(重量平均分子量/数平均分子量)は、1.0~4.0が好ましく、1.1~2.5がより好ましい。 The weight average molecular weight of the acid-reactive resin in the photosensitive layer is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 35,000 or more. The upper limit is not particularly defined, but is preferably 100,000 or less, may be 70,000 or less, and may be 50,000 or less.
Further, the amount of the component having a weight average molecular weight of 1,000 or less contained in the acid-reactive resin is preferably 10% by mass or less, more preferably 5% by mass or less of the total acid-reactive resin component. By setting it as such a structure, the sensitivity fluctuation between resin production lots can be reduced more effectively.
The dispersity (weight average molecular weight / number average molecular weight) of the acid-reactive resin is preferably 1.0 to 4.0, more preferably 1.1 to 2.5.
感光層は、その露光部が有機溶剤を含む現像液に対して難溶であることが好ましい。難溶とは、露光部が現像液に溶けにくいことをいい、具体的には、波長365nm(i線)、波長248nm(KrF線)および波長193nm(ArF線)の少なくとも1つにおいて50mJ/cm2以上の照射量で露光することによって極性が変化し、sp値(溶解パラメータ値)が19(MPa)1/2未満の溶剤に対して難溶となることが好ましく、18.5(MPa)1/2以下の溶剤に対して難溶となることがより好ましく、18.0(MPa)1/2以下の溶剤に対して難溶となることがさらに好ましい。さらに、波長365nm(i線)、波長248nm(KrF線)および波長193nm(ArF線)の少なくとも1つにおいて50~250mJ/cm2の照射量で露光することによって、上記のとおり極性が変化することがより好ましい。 The content of the acid reactive resin in the photosensitive layer is preferably 20 to 99.9% by mass, more preferably 40 to 99% by mass, and further preferably 70 to 99% by mass. 1 type, or 2 or more types of acid reactive resin may be contained. When using 2 or more types, it is preferable that a total amount becomes the said range.
The photosensitive layer is preferably hardly soluble in a developing solution containing an organic solvent in the exposed portion. Slightly soluble means that the exposed portion is hardly soluble in the developer, and specifically, 50 mJ / cm at least one of a wavelength of 365 nm (i-line), a wavelength of 248 nm (KrF line) and a wavelength of 193 nm (ArF line). It is preferable that the polarity changes due to exposure at an irradiation dose of 2 or more, and the sp value (solubility parameter value) is hardly soluble in a solvent of less than 19 (MPa) 1/2 , and 18.5 (MPa) It is more preferable that it is hardly soluble in a solvent of 1/2 or less, and it is more preferable that it is hardly soluble in a solvent of 18.0 (MPa) 1/2 or less. Furthermore, the polarity changes as described above by exposing at a dose of 50 to 250 mJ / cm 2 at at least one of a wavelength of 365 nm (i-line), a wavelength of 248 nm (KrF line) and a wavelength of 193 nm (ArF line). Is more preferable.
感光層の厚さは、解像力向上の観点から、0.1μm以上が好ましく、0.5μm以上がより好ましく、0.75μm以上がさらに好ましく、0.8μm以上が特に好ましい。感光層の厚さの上限値としては、10μm以下が好ましく、5.0μm以下がより好ましく、2.0μm以下がさらに好ましい。
さらに、感光層と水溶性樹脂層との厚さの合計が、0.2μm以上であることが好ましく、1.0μm以上であることがより好ましく、2.0μm以上であることがさらに好ましい。上限値としては、20.0μm以下であることが好ましく、10.0μm以下であることがより好ましく、5.0μm以下であることがさらに好ましい。 The photosensitive layer may be a negative photosensitive layer or a positive photosensitive layer, but a negative photosensitive layer is preferable because it enables formation of finer trenches and hole patterns. . Furthermore, the negative photosensitive layer can more effectively suppress organic defects.
The thickness of the photosensitive layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, further preferably 0.75 μm or more, and particularly preferably 0.8 μm or more from the viewpoint of improving the resolution. The upper limit of the thickness of the photosensitive layer is preferably 10 μm or less, more preferably 5.0 μm or less, and further preferably 2.0 μm or less.
Furthermore, the total thickness of the photosensitive layer and the water-soluble resin layer is preferably 0.2 μm or more, more preferably 1.0 μm or more, and further preferably 2.0 μm or more. The upper limit is preferably 20.0 μm or less, more preferably 10.0 μm or less, and even more preferably 5.0 μm or less.
酸反応性樹脂は、感光性樹脂組成物を構成する樹脂成分であり、酸の作用により酢酸ブチルに対する溶解速度が変化する。
本発明における酸反応性樹脂は、通常、酸によって解離する基を含む構成単位を含む樹脂であり、他の構成単位を含んでいてもよい。 << Dissolution rate >>
The acid-reactive resin is a resin component constituting the photosensitive resin composition, and the dissolution rate in butyl acetate is changed by the action of an acid.
The acid-reactive resin in the present invention is usually a resin containing a structural unit containing a group dissociated by an acid, and may contain another structural unit.
酸反応性樹脂のsp値が18.0(MPa)1/2以下の有機溶剤への溶解速度は、40nm/秒以上であることがより好ましい。また、酸反応性樹脂の酸分解性基が分解したときには、sp値が18.0(MPa)1/2以下の有機溶剤への溶解速度は1nm/秒未満であることがより好ましい。
酸反応性樹脂は、また、sp値(溶解パラメータ値)が18.0(MPa)1/2以下の有機溶剤に可溶で、かつ、下記式(1)で表される構成単位におけるテトラヒドロフラニル基が分解または解離したときにsp値が18.0(MPa)1/2以下の有機溶剤に難溶となる樹脂であることが好ましい。
ここで、「sp値(溶解パラメータ値)が18.0(MPa)1/2以下の有機溶剤に可溶」とは、化合物(樹脂)の溶液を基板上に塗布し、100℃で1分間加熱することによって形成される化合物(樹脂)の塗膜(厚さ1μm)の、23℃における酢酸ブチルに対する溶解速度が、20nm/秒以上であることをいい、「sp値が18.0(MPa)1/2以下の有機溶剤に難溶」とは、化合物(樹脂)の溶液を基板上に塗布し、100℃で1分間加熱することによって形成される化合物(樹脂)の塗膜(厚さ1μm)の、23℃における酢酸ブチルに対する溶解速度が、10nm/秒未満であることをいう。 In the present invention, the acid-reactive resin is a resin whose dissolution rate with respect to butyl acetate is changed by the action of an acid, and this change is more preferably a decrease in the dissolution rate.
The dissolution rate of the acid-reactive resin in an organic solvent having an sp value of 18.0 (MPa) 1/2 or less is more preferably 40 nm / second or more. Further, when the acid-decomposable group of the acid-reactive resin is decomposed, the dissolution rate in an organic solvent having an sp value of 18.0 (MPa) 1/2 or less is more preferably less than 1 nm / second.
The acid-reactive resin is also soluble in an organic solvent having an sp value (solubility parameter value) of 18.0 (MPa) 1/2 or less, and tetrahydrofuranyl in a structural unit represented by the following formula (1) A resin that is hardly soluble in an organic solvent having a sp value of 18.0 (MPa) 1/2 or less when the group is decomposed or dissociated is preferable.
Here, “sp value (solubility parameter value) is 18.0 (MPa) soluble in an organic solvent of 1/2” or less means that a solution of a compound (resin) is applied on a substrate, and then at 100 ° C. for 1 minute. The dissolution rate of the coating film (
酸反応性樹脂は、アクリル系重合体であることが好ましい。
「アクリル系重合体」は、付加重合型の樹脂であり、(メタ)アクリル酸またはそのエステルに由来する構成単位を含む重合体であり、(メタ)アクリル酸またはそのエステルに由来する構成単位以外の構成単位、例えば、スチレン類に由来する構成単位やビニル化合物に由来する構成単位等を含んでいてもよい。アクリル系重合体は、(メタ)アクリル酸またはそのエステルに由来する構成単位を、重合体における全構成単位に対し、50モル%以上有することが好ましく、80モル%以上有することがより好ましく、(メタ)アクリル酸またはそのエステルに由来する構成単位のみからなる重合体であることが特に好ましい。このようなアクリル系重合体は、ネガ型現像に好ましく用いられる。 << Acid reactive resin >>
The acid-reactive resin is preferably an acrylic polymer.
“Acrylic polymer” is an addition polymerization type resin, which is a polymer containing a structural unit derived from (meth) acrylic acid or an ester thereof, and other than a structural unit derived from (meth) acrylic acid or an ester thereof. These structural units may include, for example, structural units derived from styrenes, structural units derived from vinyl compounds, and the like. The acrylic polymer preferably has a structural unit derived from (meth) acrylic acid or an ester thereof in an amount of 50 mol% or more, more preferably 80 mol% or more, based on all the structural units in the polymer. Particularly preferred is a polymer consisting only of structural units derived from (meth) acrylic acid or its ester. Such an acrylic polymer is preferably used for negative development.
L1は、カルボニル基またはフェニレン基を表し、カルボニル基であることが好ましい。
R1~R7はそれぞれ独立に、水素原子またはアルキル基を表す。R1~R7におけるアルキル基は、R8と同義であり、好ましい態様も同様である。また、R1~R7のうち、1つ以上が水素原子であることが好ましく、R1~R7の全てが水素原子であることがより好ましい。 The acid-reactive resin preferably has a cyclic ether ester structure, and more preferably has a structure represented by the following formula (1).
L 1 represents a carbonyl group or a phenylene group, and is preferably a carbonyl group.
R 1 to R 7 each independently represents a hydrogen atom or an alkyl group. The alkyl group in R 1 to R 7 has the same meaning as R 8 , and the preferred embodiment is also the same. Further, among the
酸反応性樹脂は、架橋性基を有する構成単位(構成単位(3))を含んでいる態様も好ましいが、架橋性基を有する構成単位(3)を実質的に含まない構成とすることが好ましい。このような構成とすることにより、パターニング後に、感光層をより効果的に除去することが可能になる。ここで、実質的にとは、例えば、酸反応性樹脂の全構成単位の3モル%以下をいい、好ましくは1モル%以下をいう。 The acrylic polymer may contain a structural unit having a crosslinkable group. Details of the crosslinkable group can be referred to the descriptions in paragraph numbers 0032 to 0046 of JP2011-209692A, the contents of which are incorporated herein.
Although the aspect in which the acid-reactive resin contains the structural unit (structural unit (3)) having a crosslinkable group is also preferable, the acid-reactive resin may have a configuration that does not substantially contain the structural unit (3) having a crosslinkable group. preferable. With such a configuration, the photosensitive layer can be more effectively removed after patterning. Here, “substantially” means, for example, 3 mol% or less, preferably 1 mol% or less of all structural units of the acid-reactive resin.
構成単位(4)は、1種または2種以上を組み合わせて使用することができる。アクリル系重合体を構成する全モノマー単位中、構成単位(4)を含有させる場合における構成単位(4)を形成するモノマー単位の含有率は、1~60モル%が好ましく、5~50モル%がより好ましく、5~40モル%がさらに好ましい。2種以上用いる場合、合計量が上記範囲となることが好ましい。 The acid-reactive resin may contain other structural units (structural unit (4)). Examples of the radical polymerizable monomer used for forming the structural unit (4) include compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623. As a preferred example of the structural unit (4), a structural unit derived from at least one selected from the group consisting of a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene, and an N-substituted maleimide. Is mentioned. Among these, benzyl (meth) acrylate, (meth) acrylic acid tricyclo [5.2.1.02,6] decan-8-yl, (meth) acrylic acid tricyclo [5.2.1.02,6] Decan-8-yloxyethyl, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid ester containing alicyclic structure such as 2-methylcyclohexyl (meth) acrylate, or styrene Such hydrophobic monomers are preferred.
The structural unit (4) can be used alone or in combination of two or more. The content of the monomer unit forming the structural unit (4) in the case where the structural unit (4) is included in all monomer units constituting the acrylic polymer is preferably 1 to 60 mol%, and 5 to 50 mol%. Is more preferable, and 5 to 40 mol% is more preferable. When using 2 or more types, it is preferable that a total amount becomes the said range.
酸反応性樹脂としては、不飽和多価カルボン酸無水物類を共重合させた前駆共重合体中の酸無水物基に、2,3-ジヒドロフランを、酸触媒の不存在下、室温(25℃)~100℃程度の温度で付加させることにより得られる共重合体も好ましい。
以下の樹脂も酸反応性樹脂の好ましい例として挙げられる。
BzMA/THFMA/t-BuMA(モル比:20~60:35~65:5~30)
BzMA/THFAA/t-BuMA(モル比:20~60:35~65:5~30)
BzMA/THPMA/t-BuMA(モル比:20~60:35~65:5~30)
BzMA/PEES/t-BuMA(モル比:20~60:35~65:5~30)
BzMAは、ベンジルメタクリレートであり、THFMAは、テトラヒドロフラン-2-イル メタクリレートであり、BuMAは、ブチルメタクリレートであり、THFAAは、テトラヒドロフラン-2-イル アクリレートであり、THPMAは、テトラヒドロ-2H-ピラン-2-イル メタクリレートであり、PEESは、p-エトキシエトキシスチレンである。 Various methods are known for synthesizing acrylic polymers. For example, radical polymerizable monomers used to form at least the structural unit (1), the structural unit (2), etc. It can be synthesized by polymerizing a radically polymerizable monomer mixture containing a radical polymerization initiator in an organic solvent.
As the acid-reactive resin, 2,3-dihydrofuran is added at room temperature (in the absence of an acid catalyst) to the acid anhydride group in the precursor copolymer obtained by copolymerizing unsaturated polyvalent carboxylic acid anhydrides. A copolymer obtained by addition at a temperature of about 25 ° C. to 100 ° C. is also preferable.
The following resins are also listed as preferred examples of the acid-reactive resin.
BzMA / THFMA / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
BzMA / THFAA / t-BuMA (molar ratio: 20 to 60:35 to 65: 5 to 30)
BzMA / THPMA / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
BzMA / PEES / t-BuMA (molar ratio: 20-60: 35-65: 5-30)
BzMA is benzyl methacrylate, THFMA is tetrahydrofuran-2-yl methacrylate, BuMA is butyl methacrylate, THFAA is tetrahydrofuran-2-yl acrylate, and THPMA is tetrahydro-2H-pyran-2. -Yl methacrylate, PEES is p-ethoxyethoxystyrene.
感光性樹脂組成物は、光酸発生剤を含んでもよい。光酸発生剤は、波長365nmに吸収を有する光酸発生剤であることが好ましい。
光酸発生剤は、オキシムスルホネート基を有する化合物(以下、単にオキシムスルホネート化合物ともいう)であることが好ましい。 << Photoacid generator >>
The photosensitive resin composition may contain a photoacid generator. The photoacid generator is preferably a photoacid generator having absorption at a wavelength of 365 nm.
The photoacid generator is preferably a compound having an oxime sulfonate group (hereinafter also simply referred to as an oxime sulfonate compound).
m3は、0~3の整数を表し、0または1が好ましい。m3が2または3であるとき、複数のX3は同一でも異なっていてもよい。
R34は、アルキル基またはアリール基を表し、炭素数1~10のアルキル基、炭素数1~10のアルコキシル基、炭素数1~5のハロゲン化アルキル基、炭素数1~5のハロゲン化アルコキシル基、Wで置換されていてもよいフェニル基、Wで置換されていてもよいナフチル基またはWで置換されていてもよいアントラニル基であることが好ましい。Wは、ハロゲン原子、シアノ基、ニトロ基、炭素数1~10のアルキル基、炭素数1~10のアルコキシル基、炭素数1~5のハロゲン化アルキル基または炭素数1~5のハロゲン化アルコキシル基、炭素数6~20のアリール基、炭素数6~20のハロゲン化アリール基を表す。 The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group. However, the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS- It is preferable that it is an oxime sulfonate compound represented by 105).
m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, the plurality of X 3 may be the same or different.
R 34 represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxyl group having 1 to 5 carbon atoms. And a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxyl group having 1 to 5 carbon atoms. Group, an aryl group having 6 to 20 carbon atoms, and a halogenated aryl group having 6 to 20 carbon atoms.
R11で表されるアルキル基、アリール基またはヘテロアリール基は、置換基を有していてもよい。R11で表されるアルキル基としては、置換基を有していてもよい総炭素数1~30のアルキル基であることが好ましい。R11で表されるアルキル基が有していてもよい置換基としては、ハロゲン原子、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アミノカルボニル基が挙げられる。R11で表されるアルキル基としては、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、s-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基、n-オクチル基、n-デシル基、n-ドデシル基、トリフルオロメチル基、パーフルオロプロピル基、パーフルオロヘキシル基、ベンジル基などが挙げられる。
また、R11で表されるアリール基としては、置換基を有してもよい総炭素数6~30のアリール基が好ましい。R11で表されるアリール基が有していてもよい置換基としては、ハロゲン原子、アルキル基、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アミノカルボニル基、スルホン酸基、アミノスルホニル基、アルコキシスルホニル基が挙げられる。R11で表されるアリール基としては、フェニル基、p-メチルフェニル基、p-クロロフェニル基、ペンタクロロフェニル基、ペンタフルオロフェニル基、o-メトキシフェニル基、p-フェノキシフェニル基が好ましい。また、R11で表されるヘテロアリール基としては、置換基を有してもよい総炭素数4~30のヘテロアリール基が好ましい。R11で表されるヘテロアリール基が有していてもよい置換基としては、ハロゲン原子、アルキル基、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アミノカルボニル基、スルホン酸基、アミノスルホニル基、アルコキシスルホニル基が挙げられる。R11で表されるヘテロアリール基は、少なくとも1つの複素芳香環を有していればよく、例えば、複素芳香環とベンゼン環とが縮環していてもよい。R11で表されるヘテロアリール基としては、置換基を有していてもよい、チオフェン環、ピロール環、チアゾール環、イミダゾール環、フラン環、ベンゾチオフェン環、ベンゾチアゾール環、および、ベンゾイミダゾール環よりなる群から選ばれた環から1つの水素原子を除いた基が挙げられる。 Specific examples of the oxime sulfonate compound represented by the formula (OS-1) include the following compounds described in paragraph numbers 0064 to 0068 of JP2011-209692A, the contents of which are described in the present specification. Incorporated into.
The alkyl group, aryl group or heteroaryl group represented by R 11 may have a substituent. The alkyl group represented by R 11 is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent. Examples of the substituent that the alkyl group represented by R 11 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Is mentioned. Examples of the alkyl group represented by R 11 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, and n-hexyl. Group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group and the like.
In addition, the aryl group represented by R 11 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent. Examples of the substituent that the aryl group represented by R 11 may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, Examples thereof include an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group. The aryl group represented by R 11 is preferably a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group. The heteroaryl group represented by R 11 is preferably a heteroaryl group having 4 to 30 carbon atoms which may have a substituent. Examples of the substituent that the heteroaryl group represented by R 11 may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, and an aryloxycarbonyl group. , An aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group. The heteroaryl group represented by R 11 only needs to have at least one heteroaromatic ring. For example, the heteroaromatic ring and the benzene ring may be condensed. Examples of the heteroaryl group represented by R 11 include a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring, which may have a substituent. And a group obtained by removing one hydrogen atom from a ring selected from the group consisting of:
化合物中に2以上存在する場合のあるR12のうち、1つまたは2つがアルキル基、アリール基またはハロゲン原子であることが好ましく、1つがアルキル基、アリール基またはハロゲン原子であることがより好ましく、1つがアルキル基であり、かつ残りが水素原子であることが特に好ましい。
R12で表されるアルキル基またはアリール基は、置換基を有していてもよい。
R12で表されるアルキル基またはアリール基が有していてもよい置換基としては、上記Wを例示することができる。
R12で表されるアルキル基としては、置換基を有してもよい総炭素数1~12のアルキル基であることが好ましく、置換基を有してもよい総炭素数1~6のアルキル基であることがより好ましい。
R12で表されるアルキル基としては、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、s-ブチル基、n-ヘキシル基、アリル基、クロロメチル基、ブロモメチル基、メトキシメチル基、ベンジル基が好ましく、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、s-ブチル基、n-ヘキシル基がより好ましく、メチル基、エチル基、n-プロピル基、n-ブチル基、n-ヘキシル基がさらに好ましく、メチル基が特に好ましい。
R12で表されるアリール基としては、置換基を有してもよい総炭素数6~30のアリール基であることが好ましい。
R12で表されるアリール基としては、フェニル基、p-メチルフェニル基、o-クロロフェニル基、p-クロロフェニル基、o-メトキシフェニル基、p-フェノキシフェニル基が好ましい。
R12で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。これらの中でも、塩素原子、臭素原子が好ましい。
XはOまたはSを表し、Oであることが好ましい。上記式(OS-103)~(OS-105)において、Xを環員として含む環は、5員環または6員環である。 R 12 is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
Of R 12 which may be present in the compound in two or more, one or two are preferably an alkyl group, an aryl group or a halogen atom, more preferably one is an alkyl group, an aryl group or a halogen atom. It is particularly preferred that one is an alkyl group and the rest are hydrogen atoms.
The alkyl group or aryl group represented by R 12 may have a substituent.
Examples of the substituent that the alkyl group or aryl group represented by R 12 may have include the above W.
The alkyl group represented by R 12 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and an alkyl group having 1 to 6 carbon atoms which may have a substituent. More preferably, it is a group.
Examples of the alkyl group represented by R 12 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, A chloromethyl group, a bromomethyl group, a methoxymethyl group, and a benzyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group. A group is more preferable, a methyl group, an ethyl group, an n-propyl group, an n-butyl group and an n-hexyl group are more preferable, and a methyl group is particularly preferable.
The aryl group represented by R 12 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
The aryl group represented by R 12 is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
Examples of the halogen atom represented by R 12 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.
X represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
R16で表されるアルキル基およびアルキルオキシ基は、置換基を有していてもよい。
R16で表されるアルキル基としては、置換基を有していてもよい総炭素数1~30のアルキル基であることが好ましい。
R16で表されるアルキル基が有していてもよい置換基としては、ハロゲン原子、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アミノカルボニル基が挙げられる。
R16で表されるアルキル基としては、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、s-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基、n-オクチル基、n-デシル基、n-ドデシル基、トリフルオロメチル基、パーフルオロプロピル基、パーフルオロヘキシル基、ベンジル基が好ましい。
R16で表されるアルキルオキシ基としては、置換基を有してもよい総炭素数1~30のアルキルオキシ基であることが好ましい。
R16で表されるアルキルオキシ基が有していてもよい置換基としては、ハロゲン原子、アルキルオキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アミノカルボニル基が挙げられる。
R16で表されるアルキルオキシ基としては、メチルオキシ基、エチルオキシ基、ブチルオキシ基、ヘキシルオキシ基、フェノキシエチルオキシ基、トリクロロメチルオキシ基、または、エトキシエチルオキシ基が好ましい。
R16におけるアミノスルホニル基としては、メチルアミノスルホニル基、ジメチルアミノスルホニル基、フェニルアミノスルホニル基、メチルフェニルアミノスルホニル基、アミノスルホニル基が挙げられる。
R16で表されるアルコキシスルホニル基としては、メトキシスルホニル基、エトキシスルホニル基、プロピルオキシスルホニル基、ブチルオキシスルホニル基が挙げられる。
msは0~6の整数を表し、0~2の整数であることが好ましく、0または1であることがより好ましく、0であることが特に好ましい。 ns represents 1 or 2, and when X is O, ns is preferably 1, and when X is S, ns is preferably 2.
The alkyl group and alkyloxy group represented by R 16 may have a substituent.
The alkyl group represented by R 16 is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyl group represented by R 16 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Is mentioned.
Examples of the alkyl group represented by R 16 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, and n-hexyl. Group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group and benzyl group are preferred.
The alkyloxy group represented by R 16 is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyloxy group represented by R 16 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl. Groups.
The alkyloxy group represented by R 16 is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group.
Examples of the aminosulfonyl group for R 16 include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group.
Examples of the alkoxysulfonyl group represented by R 16 include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.
ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.
R17は、水素原子または臭素原子を表し、水素原子であることが好ましい。
R18は、水素原子、炭素数1~8のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基またはクロロフェニル基を表し、炭素数1~8のアルキル基、ハロゲン原子またはフェニル基であることが好ましく、炭素数1~8のアルキル基であることがより好ましく、炭素数1~6のアルキル基であることがさらに好ましく、メチル基であることが特に好ましい。
R19は、水素原子、ハロゲン原子、メチル基またはメトキシ基を表し、水素原子であることが好ましい。
R20は、水素原子またはメチル基を表し、水素原子であることが好ましい。
また、上記オキシムスルホネート化合物において、オキシムの立体構造(E,Z)については、どちらか一方であっても、混合物であってもよい。
上記式(OS-103)~(OS-105)で表されるオキシムスルホネート化合物の具体例としては、特開2011-209692号公報の段落番号0088~0095に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。 The compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), (OS-110) or (OS-111). The compound represented by OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108). ) Or (OS-109) is particularly preferable.
R 17 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R 18 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, and an alkyl group having 1 to 8 carbon atoms, A halogen atom or a phenyl group is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is further preferable, and a methyl group is particularly preferable.
R 19 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R 20 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the oxime sulfonate compound, the oxime steric structure (E, Z) may be either one or a mixture.
Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include the compounds described in paragraph numbers 0088 to 0095 of JP 2011-209692 A, and their contents Are incorporated herein.
R12aは、アルキル基またはアリール基を表す。
Xは、-O-、-S-、-NH-、-NR15-、-CH2-、-CR16H-または-CR16R17-を表し、R15~R17はそれぞれ独立に、アルキル基またはアリール基を表す。
R21~R24はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシル基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基またはアリール基を表す。R21~R24のうちの2つがそれぞれ互いに結合して環を形成してもよい。このとき、環が縮環してベンゼン環ともに縮合環を形成していてもよい。
R21~R24としては、水素原子、ハロゲン原子またはアルキル基が好ましく、また、R21~R24のうちの少なくとも2つが互いに結合してアリール基を形成する態様も好ましい。中でも、R21~R24がいずれも水素原子である態様が好ましい。
上記した置換基は、いずれも、さらに置換基を有していてもよい。
上記式(OS-101)で表される化合物は、式(OS-102)で表される化合物であることがより好ましい。 Other preferred embodiments of the oxime sulfonate compound having at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
R 12a represents an alkyl group or an aryl group.
X is, -O -, - S -, - NH -, - NR 15 -, - CH 2 -, - CR 16 H- or -CR 16 R 17 - represents, in each of R 15 ~ R 17 independently, Represents an alkyl group or an aryl group.
R 21 to R 24 are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group or aryl. Represents a group. Two of R 21 to R 24 may be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
R 21 to R 24 are preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R 21 to R 24 are bonded to each other to form an aryl group is also preferred. Of these, an embodiment in which R 21 to R 24 are all hydrogen atoms is preferred.
Any of the above-described substituents may further have a substituent.
The compound represented by the formula (OS-101) is more preferably a compound represented by the formula (OS-102).
式(OS-101)で表される化合物の具体例としては、特開2011-209692号公報の段落番号0102~0106に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。
上記化合物の中でも、b-9、b-16、b-31、b-33が好ましい。
市販品としては、WPAG-336(和光純薬工業(株)製)、WPAG-443(、和光純薬工業(株)製)、MBZ-101(みどり化学(株)製)等を挙げることができる。 In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include compounds described in paragraph numbers 0102 to 0106 of JP2011-209692A, the contents of which are incorporated herein.
Among the above compounds, b-9, b-16, b-31 and b-33 are preferable.
Examples of commercially available products include WPAG-336 (manufactured by Wako Pure Chemical Industries, Ltd.), WPAG-443 (manufactured by Wako Pure Chemical Industries, Ltd.), MBZ-101 (manufactured by Midori Chemical Co., Ltd.), and the like. it can.
これに対して、オキシムスルホネート化合物は、活性光線に感応して生成する酸が保護された酸基の脱保護に対して触媒として作用するので、1個の光量子の作用で生成した酸が、多数の脱保護反応に寄与し、量子収率は1を超え、例えば、10の数乗のような大きい値となり、いわゆる化学増幅の結果として、高感度が得られると推測される。
また、オキシムスルホネート化合物は、広がりのあるπ共役系を有しているため、長波長側にまで吸収を有しており、遠紫外線(DUV)、ArF線、KrF線、i線のみならず、g線においても非常に高い感度を示す。
上記酸反応性樹脂における酸分解性基としてテトラヒドロフラニル基を用いることにより、アセタールまたはケタールに比べ同等またはそれ以上の酸分解性を得ることができる。これにより、より短時間のポストベークで確実に酸分解性基を消費することができる。さらに、光酸発生剤であるオキシムスルホネート化合物を組み合わせて用いることで、スルホン酸発生速度が上がるため、酸の生成が促進され、樹脂の酸分解性基の分解が促進される。また、オキシムスルホネート化合物が分解することで得られる酸は、分子の小さいスルホン酸であることから、硬化膜中での拡散性も高く、より高感度化することができる。
光酸発生剤は、感光性樹脂組成物の全固形分に対して、0.1~20質量%使用することが好ましく、0.5~18質量%使用することがより好ましく、0.5~10質量%使用することがさらに好ましく、0.5~3質量%使用することが一層好ましく、0.5~1.2質量%使用することがより一層好ましい。
光酸発生剤は、1種を単独で使用しても、2種以上を併用してもよい。2種以上用いる場合、合計量が上記範囲となることが好ましい。 As the photoacid generator sensitive to actinic rays, those which do not contain a 1,2-quinonediazide compound are preferred. The reason is that the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is 1 or less and is less sensitive than the oxime sulfonate compound.
In contrast, the oxime sulfonate compound acts as a catalyst for the deprotection of an acid group protected in response to an actinic ray, so that a large number of acids generated by the action of one photon are present. It contributes to the deprotection reaction, and the quantum yield exceeds 1, for example, a large value such as a power of 10, and it is estimated that high sensitivity is obtained as a result of so-called chemical amplification.
In addition, since the oxime sulfonate compound has a broad π-conjugated system, it has absorption up to the long wavelength side, and not only deep ultraviolet rays (DUV), ArF rays, KrF rays, i rays, It shows very high sensitivity even in the g-line.
By using a tetrahydrofuranyl group as an acid-decomposable group in the acid-reactive resin, an acid-decomposability equivalent to or higher than that of an acetal or ketal can be obtained. Thereby, an acid-decomposable group can be consumed reliably in a shorter post-bake. Furthermore, by using the oxime sulfonate compound that is a photoacid generator in combination, the sulfonic acid generation rate is increased, so that the generation of acid is accelerated and the decomposition of the acid-decomposable group of the resin is accelerated. Moreover, since the acid obtained by decomposing | disassembling an oxime sulfonate compound is a sulfonic acid with a small molecule | numerator, the diffusibility in a cured film is also high, and it can make more highly sensitive.
The photoacid generator is preferably used in an amount of 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, based on the total solid content of the photosensitive resin composition. It is further preferable to use 10% by mass, more preferably 0.5 to 3% by mass, and still more preferably 0.5 to 1.2% by mass.
A photo-acid generator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types, it is preferable that a total amount becomes the said range.
感光性樹脂組成物には、その他の成分を含有することができる。
その他の成分としては、塗布性の観点から有機溶剤を含有することが好ましい。
<<有機溶剤>>
感光性樹脂組成物は、有機溶剤を含有することが好ましく、酸反応性樹脂の他、光酸発生剤、および、各種添加剤の任意成分を、有機溶剤に溶解した溶液として調製されることが好ましい。
感光性樹脂組成物に使用される有機溶剤としては、公知の有機溶剤を用いることができ、エチレングリコールモノアルキルエーテル類、エチレングリコールジアルキルエーテル類、エチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールジアルキルエーテル類、プロピレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジアルキルエーテル類、ジエチレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、ジプロピレングリコールモノアルキルエーテルアセテート類、エステル類、ケトン類、アミド類、ラクトン類等が例示できる。
有機溶剤としては、例えば、(1)エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル等のエチレングリコールモノアルキルエーテル類;(2)エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジプロピルエーテル等のエチレングリコールジアルキルエーテル類;(3)エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノプロピルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類;(4)プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等のプロピレングリコールモノアルキルエーテル類;(5)プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル等のプロピレングリコールジアルキルエーテル類;(6)プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類;(7)ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル等のジエチレングリコールジアルキルエーテル類;(8)ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノプロピルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート等のジエチレングリコールモノアルキルエーテルアセテート類;(9)ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル等のジプロピレングリコールモノアルキルエーテル類;(10)ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、ジプロピレングリコールエチルメチルエーテル等のジプロピレングリコールジアルキルエーテル類;(11)ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノプロピルエーテルアセテート、ジプロピレングリコールモノブチルエーテルアセテート等のジプロピレングリコールモノアルキルエーテルアセテート類;(12)乳酸メチル、乳酸エチル、乳酸n-プロピル、乳酸イソプロピル、乳酸n-ブチル、乳酸イソブチル、乳酸n-アミル、乳酸イソアミル等の乳酸エステル類;(13)酢酸n-ブチル、酢酸イソブチル、酢酸n-アミル、酢酸イソアミル、酢酸n-ヘキシル、酢酸2-エチルヘキシル、プロピオン酸エチル、プロピオン酸n-プロピル、プロピオン酸イソプロピル、プロピオン酸n-ブチル、プロピオン酸イソブチル、酪酸メチル、酪酸エチル、酪酸n-プロピル、酪酸イソプロピル、酪酸n-ブチル、酪酸イソブチル等の脂肪族カルボン酸エステル類;(14)ヒドロキシ酢酸エチル、2-ヒドロキシ-2-メチルプロピオン酸エチル、2-ヒドロキシ-3-メチル酪酸エチル、メトキシ酢酸エチル、エトキシ酢酸エチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、3-メトキシブチルアセテート、3-メチル-3-メトキシブチルアセテート、3-メチル-3-メトキシブチルプロピオネート、3-メチル-3-メトキシブチルブチレート、アセト酢酸メチル、アセト酢酸エチル、ピルビン酸メチル、ピルビン酸エチル等の他のエステル類;(15)メチルエチルケトン、メチルプロピルケトン、メチル-n-ブチルケトン、メチルイソブチルケトン、2-ヘプタノン、3-ヘプタノン、4-ヘプタノン、シクロヘキサノン等のケトン類;(16)N-メチルホルムアミド、N,N-ジメチルホルムアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等のアミド類;(17)γ-ブチロラクトン等のラクトン類等を挙げることができる。
また、これらの有機溶剤にさらに必要に応じて、ベンジルエチルエーテル、ジヘキシルエーテル、エチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、イソホロン、カプロン酸、カプリル酸、1-オクタノール、1-ノナノール、ベンジルアルコール、アニソール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、炭酸エチレン、炭酸プロピレン等の有機溶剤を添加することもできる。
上記した有機溶剤のうち、プロピレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジアルキルエーテル類、または両者の組合せが好ましく、ジエチレングリコールエチルメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、または両者の組合せが特に好ましい。
これら有機溶剤は、1種を単独で、または2種以上を混合して使用することができる。
2種以上用いる場合、合計量が上記範囲となることが好ましい。
さらに、液保存安定性の観点から、感光性樹脂組成物が、塩基性化合物を含有することが好ましく、塗布性の観点から界面活性剤を含有することが好ましい。 << Other ingredients >>
The photosensitive resin composition can contain other components.
As other components, an organic solvent is preferably contained from the viewpoint of coatability.
<< Organic solvent >>
The photosensitive resin composition preferably contains an organic solvent, and may be prepared as a solution in which an optional component of a photoacid generator and various additives in addition to an acid-reactive resin is dissolved in an organic solvent. preferable.
As the organic solvent used in the photosensitive resin composition, known organic solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether. , Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetate , Esters, ketones, amides, lactones and the like.
Examples of the organic solvent include (1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; (2) ethylene glycol dimethyl ether, ethylene glycol diethyl Ethylene glycol dialkyl ethers such as ether and ethylene glycol dipropyl ether; (3) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate Acetates; (4) propylene glycol Propylene glycol monoalkyl ethers such as monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; (5) Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether and propylene glycol diethyl ether; (6) Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; (7) diethylene glycol dimethyl ether, diethylene glycol diethyl ether, die Diethylene glycol dialkyl ethers such as lenglycol ethyl methyl ether; (8) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate; (9) dipropylene Dipropylene glycol monoalkyl ethers such as glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether; (10) dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene (11) Dipropylene such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate (12) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate; (13) n acetate -Butyl, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, Aliphatic carboxylic acid esters such as isopropyl lopionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate; (14) ethyl hydroxyacetate , Ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate Acetoacetic acid Other esters such as chill, methyl pyruvate, ethyl pyruvate; (15) such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone Ketones; (16) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; (17) lactones such as γ-butyrolactone, etc. Can be mentioned.
In addition, these organic solvents may further contain benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-octanol, if necessary. Organic solvents such as nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate can also be added.
Of the organic solvents described above, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, or a combination of both are preferred, and diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, or a combination of both are particularly preferred.
These organic solvents can be used individually by 1 type or in mixture of 2 or more types.
When using 2 or more types, it is preferable that a total amount becomes the said range.
Furthermore, from the viewpoint of liquid storage stability, the photosensitive resin composition preferably contains a basic compound, and from the viewpoint of applicability, it preferably contains a surfactant.
感光性樹脂組成物は塩基性化合物を含有することが好ましい。
塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、および、カルボン酸の第四級アンモニウム塩等が挙げられる。
脂肪族アミンとしては、例えば、トリメチルアミン、ジエチルアミン、トリエチルアミン、ジ-n-プロピルアミン、トリ-n-プロピルアミン、ジ-n-ペンチルアミン、トリ-n-ペンチルアミン、ジエタノールアミン、トリエタノールアミン、ジシクロヘキシルアミン、ジシクロヘキシルメチルアミンなどが挙げられる。
芳香族アミンとしては、例えば、アニリン、ベンジルアミン、N,N-ジメチルアニリン、ジフェニルアミンなどが挙げられる。
複素環式アミンとしては、例えば、ピリジン、2-メチルピリジン、4-メチルピリジン、2-エチルピリジン、4-エチルピリジン、2-フェニルピリジン、4-フェニルピリジン、N-メチル-4-フェニルピリジン、4-ジメチルアミノピリジン、イミダゾール、ベンズイミダゾール、4-メチルイミダゾール、2-フェニルベンズイミダゾール、2,4,5-トリフェニルイミダゾール、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、8-オキシキノリン、ピラジン、ピラゾール、ピリダジン、プリン、ピロリジン、ピペリジン、シクロヘキシルモルホリノエチルチオウレア、ピペラジン、モルホリン、4-メチルモルホリン、1,5-ジアザビシクロ[4.3.0]-5-ノネン、1,8-ジアザビシクロ[5.3.0]-7-ウンデセンなどが挙げられる。
第四級アンモニウムヒドロキシドとしては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラ-n-ブチルアンモニウムヒドロキシド、テトラ-n-ヘキシルアンモニウムヒドロキシドなどが挙げられる。
カルボン酸の第四級アンモニウム塩としては、例えば、テトラメチルアンモニウムアセテート、テトラメチルアンモニウムベンゾエート、テトラ-n-ブチルアンモニウムアセテート、テトラ-n-ブチルアンモニウムベンゾエートなどが挙げられる。
感光性樹脂組成物が、塩基性化合物を含む場合、塩基性化合物の含有量は、酸反応性樹脂100質量部に対して、0.001~1質量部であることが好ましく、0.002~0.5質量部であることがより好ましい。
塩基性化合物は、1種を単独で使用しても、2種以上を併用してもよいが、2種以上を併用することが好ましく、2種を併用することがより好ましく、複素環式アミンを2種併用することがさらに好ましい。2種以上用いる場合、合計量が上記範囲となることが好ましい。 << basic compound >>
It is preferable that the photosensitive resin composition contains a basic compound.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.
Examples of aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, cyclohexylmorpholinoethylthiourea, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3 .0] Such as 7-undecene and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
When the photosensitive resin composition contains a basic compound, the content of the basic compound is preferably 0.001 to 1 part by mass, preferably 0.002 to 1 part by mass with respect to 100 parts by mass of the acid-reactive resin. More preferably, it is 0.5 parts by mass.
The basic compound may be used singly or in combination of two or more, preferably in combination of two or more, more preferably in combination of two, heterocyclic amine More preferably, two of these are used in combination. When using 2 or more types, it is preferable that a total amount becomes the said range.
感光性樹脂組成物は、界面活性剤を含有することが好ましい。
界面活性剤としては、アニオン系、カチオン系、ノニオン系、または、両性のいずれでも使用することができるが、好ましい界面活性剤はノニオン系界面活性剤である。
ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、フッ素系、シリコーン系界面活性剤を挙げることができる。
界面活性剤として、フッ素系界面活性剤、シリコーン系界面活性剤、または両者の組合せを含有することがより好ましい。
これらのフッ素系界面活性剤、シリコーン系界面活性剤として、例えば、特開昭62-036663号公報、特開昭61-226746号公報、特開昭61-226745号公報、特開昭62-170950号公報、特開昭63-034540号公報、特開平07-230165号公報、特開平08-062834号公報、特開平09-054432号公報、特開平09-005988号公報、特開2001-330953号公報の各公報に記載の界面活性剤を挙げることができ、市販の界面活性剤を用いることもできる。
使用できる市販の界面活性剤として、例えば、エフトップEF301、EF303(以上、新秋田化成(株)製)、フロラードFC430、431(以上、住友スリーエム(株)製)、メガファックF171、F173、F176、F189、R08(以上、DIC(株)製)、サーフロンS-382、SC101、102、103、104、105、106(以上、旭硝子(株)製)、PF-6320等のPolyFoxシリーズ(OMNOVA社製)などのフッ素系界面活性剤またはシリコーン系界面活性剤を挙げることができる。また、ポリシロキサンポリマーKP-341(信越化学工業(株)製)も、シリコーン系界面活性剤として用いることができる。 << Surfactant >>
It is preferable that the photosensitive resin composition contains a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based and silicone surfactants. .
As the surfactant, it is more preferable to contain a fluorine-based surfactant, a silicone-based surfactant, or a combination of both.
Examples of these fluorosurfactants and silicone surfactants include, for example, JP-A-62-036663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950. JP, 03-03540, JP 07-230165, JP 08-062834, 09-054432, 09-005988, 2001-330953. The surfactants described in each of the publications can be mentioned, and commercially available surfactants can also be used.
Examples of commercially available surfactants that can be used include EFTOP EF301, EF303 (above, Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (above, made by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176. , F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PF-6320, etc. PolyFox series (OMNOVA) Fluorine-based surfactant or silicone-based surfactant. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.
上記L4は、下記式(42)で表される分岐アルキレン基であることが好ましい。式(42)におけるR45は、炭素数1以上4以下のアルキル基を表し、被塗布面に対する濡れ性の点で、炭素数1以上3以下のアルキル基が好ましく、炭素数2または3のアルキル基がより好ましい。
-CH2-CH(R45)- (42)
上記共重合体の重量平均分子量は、1,500以上5,000以下であることがより好ましい。
界面活性剤を含む場合、界面活性剤の添加量は、酸反応性樹脂100質量部に対して、10質量部以下であることが好ましく、0.01~10質量部であることがより好ましく、0.01~1質量部であることがさらに好ましい。
界面活性剤は、1種を単独で、または2種以上を混合して使用することができる。2種以上用いる場合、合計量が上記範囲となることが好ましい。 In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula (41), and is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.
L 4 is preferably a branched alkylene group represented by the following formula (42). R 45 in the formula (42) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of wettability with respect to the coated surface, and an alkyl group having 2 or 3 carbon atoms. Groups are more preferred.
—CH 2 —CH (R 45 ) — (42)
The weight average molecular weight of the copolymer is more preferably 1,500 or more and 5,000 or less.
When the surfactant is included, the addition amount of the surfactant is preferably 10 parts by mass or less, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the acid-reactive resin. More preferably, the content is 0.01 to 1 part by mass.
Surfactant can be used individually by 1 type or in mixture of 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.
感光性樹脂組成物には、通常、不可避的に微量の金属不純物が含まれている。たとえば、ナトリウム、カリウム、カルシウム等のアルカリ金属またはアルカリ土類金属の塩が挙げられる。この金属不純物(特に、ナトリウム、カリウム、カルシウム)の影響により、無機系ディフェクトが生じているものと推定される。本発明では、感光性樹脂組成物中のナトリウムイオン、カリウムイオンおよびカルシウムイオンの合計含有量が、例えば、1質量ppt~1000質量ppbの範囲で、さらには50質量ppt~500質量ppbの範囲で存在するものと解される。本発明によれば、上述のとおり、適度の水分の含有により緩やかに金属不純物が系内で分散され、金属不純物の凝集を妨げ、これにより無機系ディフェクトの生成を抑止することができるものと推定される。
金属イオン量は、後述する実施例に記載の方法で測定される。 << metal impurities >>
The photosensitive resin composition usually inevitably contains a trace amount of metal impurities. For example, salts of alkali metals or alkaline earth metals such as sodium, potassium, calcium and the like can be mentioned. It is presumed that an inorganic defect occurs due to the influence of this metal impurity (especially sodium, potassium, calcium). In the present invention, the total content of sodium ion, potassium ion and calcium ion in the photosensitive resin composition is, for example, in the range of 1 mass ppt to 1000 mass ppb, and further in the range of 50 mass ppt to 500 mass ppb. It is understood that it exists. According to the present invention, as described above, it is presumed that the metal impurities are gently dispersed in the system by containing appropriate moisture, thereby preventing the aggregation of metal impurities and thereby suppressing the generation of inorganic defects. Is done.
The amount of metal ions is measured by the method described in Examples described later.
さらに、必要に応じて、酸化防止剤、可塑剤、熱ラジカル発生剤、熱酸発生剤、酸増殖剤、紫外線吸収剤、増粘剤、および、有機または無機の沈殿防止剤などの公知の添加剤を、それぞれ、1種または2種以上加えることができる。これらの詳細は、特開2011-209692号公報の段落番号0143~0148の記載を参酌でき、これらの内容は本明細書に組み込まれる。 << Other >>
Furthermore, known additions such as antioxidants, plasticizers, thermal radical generators, thermal acid generators, acid multipliers, UV absorbers, thickeners, and organic or inorganic suspending agents are added as necessary. One or more agents can be added, respectively. Details of these can be referred to the description of paragraph numbers 0143 to 0148 of JP2011-209692A, the contents of which are incorporated herein.
感光性樹脂組成物は、ポリビニルアルコール(PVA)膜上における静止接触角が、60°以下であることが好ましく、50°以下であることがより好ましく、40°以下であることがさらに好ましい。下限値としては、2°以上であることが実際的であり、5°以上であることがより実際的であり、10°以上であることがさらに実際的である。この接触角を上記範囲とすることにより、塗布均一性を改善し、濡れ性を向上できる点で好ましい。本明細書において接触角の測定方法は、後記実施例で採用した方法によるものとする。 << Static contact angle >>
In the photosensitive resin composition, the static contact angle on the polyvinyl alcohol (PVA) film is preferably 60 ° or less, more preferably 50 ° or less, and further preferably 40 ° or less. The lower limit is practically 2 ° or more, more practically 5 ° or more, and more practically 10 ° or more. By making this contact angle into the said range, it is preferable at the point which can improve application | coating uniformity and can improve wettability. In this specification, the method for measuring the contact angle is based on the method employed in the examples described later.
感光性樹脂組成物は、水溶性樹脂を含む水溶性樹脂組成物と組み合わせて、それぞれ感光層および水溶性樹脂層をこの順に形成するためのキットにしてもよい。さらには、有機半導体層加工用のキットとして用いることが好ましい。このとき、具体的態様として上述した感光性樹脂組成物の各成分および水溶性樹脂組成物の各成分を適用することが好ましい。本発明においては、さらに有機半導体形成用組成物を組み合わせたキットとしてもよい。組成物の具体的態様としては、上述した有機半導体およびその組成物の各成分を適用することが好ましい。 <Kit>
The photosensitive resin composition may be combined with a water-soluble resin composition containing a water-soluble resin to form a kit for forming a photosensitive layer and a water-soluble resin layer in this order. Furthermore, it is preferably used as a kit for processing an organic semiconductor layer. At this time, it is preferable to apply each component of the photosensitive resin composition and each component of the water-soluble resin composition described above as specific embodiments. In this invention, it is good also as a kit which combined the composition for organic-semiconductor formation further. As a specific aspect of the composition, it is preferable to apply the above-described organic semiconductor and each component of the composition.
本発明において好適に採用できるパターニング方法として下記の形態を挙げることができる。以下有機半導体層の加工(パターニング)を例にとって示すが、有機半導体層以外の層のパターニングにも利用できる。
本実施形態の有機半導体層のパターニング方法は、
(1)有機半導体層の上に、水溶性樹脂層を製膜する工程、
(2)水溶性樹脂層の有機半導体層と反対側の上に、感光層を製膜する工程、
(3)感光層を露光する工程、
(4)有機溶剤を含む現像液を用いて現像しマスクパターンを作製する工程、
(5)ドライエッチング処理にて少なくとも非マスク部の水溶性樹脂層および有機半導体層を除去する工程、
(6)水溶性樹脂層を除去する工程、
を含む。 <Organic semiconductor layer patterning method>
Examples of patterning methods that can be suitably employed in the present invention include the following forms. Hereinafter, processing (patterning) of the organic semiconductor layer will be described as an example, but it can also be used for patterning of layers other than the organic semiconductor layer.
The patterning method of the organic semiconductor layer of this embodiment is
(1) forming a water-soluble resin layer on the organic semiconductor layer;
(2) forming a photosensitive layer on the side of the water-soluble resin layer opposite to the organic semiconductor layer;
(3) a step of exposing the photosensitive layer;
(4) a step of developing using a developer containing an organic solvent to produce a mask pattern;
(5) a step of removing at least the non-masked water-soluble resin layer and the organic semiconductor layer by dry etching treatment;
(6) a step of removing the water-soluble resin layer;
including.
本実施形態の有機半導体層のパターニング方法は、有機半導体層の上に水溶性樹脂層を製膜する工程を含む。通常は、基板の上に有機半導体層を製膜した後に、本工程を行う。この場合、水溶性樹脂層は、有機半導体の基板側の面と反対側の面に製膜する。水溶性樹脂層は、通常、有機半導体層の表面に設けられるが、本発明の趣旨を逸脱しない範囲で他の層を設けてもよい。具体的には、水溶性の下塗り層等が挙げられる。また、水溶性樹脂層は1層のみ設けられていてもよいし、2層以上設けられていてもよい。水溶性樹脂層は、上述のとおり、好ましくは、水溶性樹脂組成物を用いて形成される。 << (1) Step of forming a water-soluble resin layer on the organic semiconductor layer >>
The patterning method of the organic semiconductor layer of this embodiment includes a step of forming a water-soluble resin layer on the organic semiconductor layer. Usually, this process is performed after forming an organic semiconductor layer on a substrate. In this case, the water-soluble resin layer is formed on the surface opposite to the surface of the organic semiconductor on the substrate side. The water-soluble resin layer is usually provided on the surface of the organic semiconductor layer, but other layers may be provided without departing from the spirit of the present invention. Specific examples include a water-soluble undercoat layer. Further, only one water-soluble resin layer may be provided, or two or more layers may be provided. As described above, the water-soluble resin layer is preferably formed using a water-soluble resin composition.
上記(1)の工程後、(2)水溶性樹脂層の有機半導体層側の面と反対側の上に、感光性樹脂組成物を用いて感光層を形成する。感光層は、上述のとおり、好ましくは、感光性樹脂組成物を用いて形成され、より好ましくは、酸反応性樹脂と光酸発生剤を含む、化学増幅型感光性樹脂組成物を用いて形成される。
化学増幅型感光性樹脂組成物は、光酸発生剤を含み、露光すると酸が発生し、レジストに含まれる酸反応性樹脂が反応し、パターニングが可能となり感光層として機能する。
感光性樹脂組成物の固形分濃度は、通常1.0~40質量%であり、好ましくは、10~35質量%であり、より好ましくは16~28質量%である。固形分濃度を上記範囲とすることで、感光性樹脂組成物を水溶性樹脂層上に均一に塗布することができ、さらには高解像性および矩形なプロファイルを有するレジストパターンを形成することが可能になる。固形分濃度とは、感光性樹脂組成物の総質量に対する、有機溶剤を除く他のレジスト成分の質量の百分率である。 << (2) Step of forming a photosensitive layer on the side opposite to the organic semiconductor layer of the water-soluble resin layer >>
After the step (1), a photosensitive layer is formed using a photosensitive resin composition on the side opposite to the surface of the water-soluble resin layer on the organic semiconductor layer side. As described above, the photosensitive layer is preferably formed using a photosensitive resin composition, and more preferably formed using a chemically amplified photosensitive resin composition containing an acid-reactive resin and a photoacid generator. Is done.
The chemically amplified photosensitive resin composition contains a photoacid generator. When exposed to light, an acid is generated, and the acid-reactive resin contained in the resist reacts to enable patterning and functions as a photosensitive layer.
The solid content concentration of the photosensitive resin composition is usually 1.0 to 40% by mass, preferably 10 to 35% by mass, and more preferably 16 to 28% by mass. By setting the solid content concentration in the above range, the photosensitive resin composition can be uniformly applied on the water-soluble resin layer, and further, a resist pattern having a high resolution and a rectangular profile can be formed. It becomes possible. The solid content concentration is a percentage of the mass of other resist components excluding the organic solvent with respect to the total mass of the photosensitive resin composition.
(2)工程で感光層を製膜後、上記感光層を露光する。具体的には、感光層に所定のパターンを有するマスクを介して活性光線を照射する。露光は1回のみ行ってもよく、複数回行ってもよい。
具体的には、感光性樹脂組成物の乾燥塗膜を設けた基板に、活性光線を所定のパターンで照射する。露光はマスクを介して行ってもよいし、所定のパターンを直接描画してもよい。活性光線は、好ましくは180nm以上450nm以下の波長、より好ましくは365nm(i線)、248nm(KrF線)または193nm(ArF線)の波長を有する活性光線を使用することができる。この工程の後、必要に応じて露光後加熱工程(PEB)を行ってもよい。
活性光線による露光には、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、レーザ発生装置、発光ダイオード(LED)光源などを用いることができる。
水銀灯を用いる場合には、g線(436nm)、i線(365nm)、h線(405nm)などの波長を有する活性光線を好ましく使用することができる。本発明においては、i線を用いることがその効果が好適に発揮されるため好ましい。
レーザを用いる場合には、固体(YAG)レーザでは343nm、355nmの波長が好適に用いられ、エキシマレーザでは、193nm(ArF線)、248nm(KrF線)、351nm(Xe線)が好適に用いられ、さらに半導体レーザでは375nm、405nmが好適に用いられる。この中でも、安定性、コスト等の点から355nm、405nmがより好ましい。レーザは、1回あるいは複数回に分けて、感光層に照射することができる。
露光量は、40~120mJが好ましく、60~100mJがより好ましい。
レーザの1パルス当たりのエネルギー密度は、0.1mJ/cm2以上10,000mJ/cm2以下であることが好ましい。塗膜を十分に硬化させるには、0.3mJ/cm2以上がより好ましく、0.5mJ/cm2以上がさらに好ましい。アブレーション現象により塗膜を分解させないようにするには、1,000mJ/cm2以下がより好ましく、100mJ/cm2以下がさらに好ましい。
また、パルス幅は、0.1ナノ秒(以下、「nsec」と称する)以上30,000nsec以下であることが好ましい。アブレーション現象により色塗膜を分解させないようにするには、0.5nsec以上がより好ましく、1nsec以上が一層好ましい。スキャン露光の際に合わせ精度を向上させるには、1,000nsec以下がより好ましく、50nsec以下がさらに好ましい。
レーザの周波数は、1Hz以上50,000Hz以下が好ましく、10Hz以上1,000Hz以下がより好ましい。
さらに、露光処理時間を短くするには、レーザの周波数は、10Hz以上がより好ましく、100Hz以上がさらに好ましく、スキャン露光の際に合わせ精度を向上させるには、10,000Hz以下がより好ましく、1,000Hz以下がさらに好ましい。
レーザは、水銀灯と比べると焦点を絞ることが容易であり、露光工程でのパターン形成のマスクが不要でコストダウンできるという点で好ましい。
露光装置としては、特に制限はないが、市販されているものとしては、Callisto((株)ブイ・テクノロジー製)、AEGIS((株)ブイ・テクノロジー製)、DF2200G(大日本スクリーン製造(株)製)などを使用することが可能である。また上記以外の装置も好適に用いられる。
また、必要に応じて、長波長カットフィルタ、短波長カットフィルタ、バンドパスフィルタのような分光フィルタを通して、照射光量を調整することもできる。 << (3) Step of exposing photosensitive layer >>
(2) After forming the photosensitive layer in the step, the photosensitive layer is exposed. Specifically, the photosensitive layer is irradiated with actinic rays through a mask having a predetermined pattern. Exposure may be performed only once or multiple times.
Specifically, actinic rays are irradiated in a predetermined pattern onto a substrate provided with a dry coating film of the photosensitive resin composition. Exposure may be performed through a mask, or a predetermined pattern may be drawn directly. As the actinic ray, an actinic ray having a wavelength of preferably 180 nm or more and 450 nm or less, more preferably 365 nm (i line), 248 nm (KrF line) or 193 nm (ArF line) can be used. After this step, a post-exposure heating step (PEB) may be performed as necessary.
For exposure with actinic rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, a light emitting diode (LED) light source, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. In the present invention, it is preferable to use i-line because the effect is suitably exhibited.
In the case of using a laser, wavelengths of 343 nm and 355 nm are preferably used for a solid (YAG) laser, and 193 nm (ArF line), 248 nm (KrF line), and 351 nm (Xe line) are preferably used for an excimer laser. Further, 375 nm and 405 nm are preferably used in the semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoints of stability and cost. The laser can be applied to the photosensitive layer in one or more times.
The exposure amount is preferably 40 to 120 mJ, and more preferably 60 to 100 mJ.
The energy density per pulse of the laser is preferably 0.1 mJ / cm 2 or more and 10,000 mJ / cm 2 or less. In order to sufficiently cure the coating film, 0.3 mJ / cm 2 or more is more preferable, and 0.5 mJ / cm 2 or more is more preferable. To prevent to decompose the coating film by ablation phenomenon, more preferably 1,000 mJ / cm 2 or less, 100 mJ / cm 2 or less is more preferred.
The pulse width is preferably 0.1 nanosecond (hereinafter referred to as “nsec”) or more and 30,000 nsec or less. In order to prevent the color coating film from being decomposed by the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is more preferable. In order to improve the alignment accuracy at the time of scan exposure, 1,000 nsec or less is more preferable, and 50 nsec or less is further preferable.
The frequency of the laser is preferably 1 Hz or more and 50,000 Hz or less, and more preferably 10 Hz or more and 1,000 Hz or less.
Furthermore, in order to shorten the exposure processing time, the frequency of the laser is more preferably 10 Hz or more, further preferably 100 Hz or more. More preferably, it is not more than 1,000 Hz.
The laser is preferable in that it can be easily focused as compared with a mercury lamp, and a mask for forming a pattern in the exposure process is unnecessary and the cost can be reduced.
There are no particular restrictions on the exposure apparatus, but commercially available devices include Calisto (buoy technology), AEGIS (buoy technology), DF2200G (Dainippon Screen Mfg. Co., Ltd.). Etc.) can be used. Further, devices other than those described above are also preferably used.
If necessary, the amount of irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.
(3)工程で感光層をマスクを介して露光後、有機溶剤を含む現像液(以下、有機系現像液と表すこともある)を用いて現像する。現像はネガ型が好ましい。現像液に含まれる溶剤のsp値は、19MPa1/2未満であることが好ましく、18MPa1/2以下であることがより好ましい。
現像液が含む有機溶剤としては、ケトン系溶剤、エステル系溶剤、アミド系溶剤等の極性溶剤、および炭化水素系溶剤を用いることができる。
ケトン系溶剤としては、例えば、1-オクタノン、2-オクタノン、1-ノナノン、2-ノナノン、2-ヘプタノン(メチルアミルケトン)、4-ヘプタノン、1-ヘキサノン、2-ヘキサノン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、フェニルアセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセトニルアセトン、イオノン、ジアセトニルアルコール、アセチルカービノール、アセトフェノン、メチルナフチルケトン、イソホロン、プロピレンカーボネート等を挙げることができる。
エステル系溶剤としては、例えば、酢酸メチル、酢酸ブチル、酢酸エチル、酢酸イソプロピル、酢酸ペンチル、酢酸イソペンチル、酢酸アミル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチル-3-エトキシプロピオネート、3-メトキシブチルアセテート、3-メチル-3-メトキシブチルアセテート、蟻酸メチル、蟻酸エチル、蟻酸ブチル、蟻酸プロピル、乳酸エチル、乳酸ブチル、乳酸プロピル等を挙げることができる。
アミド系溶剤としては、例えば、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、ヘキサメチルホスホリックトリアミド、1,3-ジメチル-2-イミダゾリジノン等を使用することができる。
炭化水素系溶剤としては、例えば、トルエン、キシレン等の芳香族炭化水素系溶剤、ペンタン、ヘキサン、オクタン、デカン等の脂肪族炭化水素系溶剤が挙げられる。
上記有機溶剤は、1種のみでも、2種以上用いてもよい。また、上記以外の有機溶剤と混合し使用してもよい。但し、現像液全体としての含水率が10質量%未満であることが好ましく、実質的に水分を含有しないことがより好ましい。ここでの実質的とは、例えば、現像液全体としての含水率が3質量%以下であり、より好ましくは測定限界以下であることをいう。
すなわち、有機系現像液に対する有機溶剤の使用量は、現像液の全量に対して、90質量%以上100質量%以下であることが好ましく、95質量%以上100質量%以下であることがより好ましい。
特に、有機系現像液は、ケトン系溶剤、エステル系溶剤およびアミド系溶剤からなる群より選択される少なくとも1種の有機溶剤を含有することが好ましい。
また、有機系現像液は、必要に応じて塩基性化合物を適当量含有していてもよい。塩基性化合物の例としては、上記の塩基性化合物の項で述べたものを挙げることができる。
有機系現像液の蒸気圧は、20℃において、5kPa以下であることが好ましく、3kPa以下がより好ましく、2kPa以下がさらに好ましい。有機系現像液の蒸気圧を5kPa以下にすることにより、現像液の基板上あるいは現像カップ内での蒸発が抑制され、ウェハ面内の温度均一性が向上し、結果としてウェハ面内の寸法均一性が改善する。
5kPa以下の蒸気圧を有する溶剤の具体的な例としては、1-オクタノン、2-オクタノン、1-ノナノン、2-ノナノン、2-ヘプタノン(メチルアミルケトン)、4-ヘプタノン、2-ヘキサノン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、フェニルアセトン、メチルイソブチルケトン等のケトン系溶剤、酢酸ブチル、酢酸ペンチル、酢酸イソペンチル、酢酸アミル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチル-3-エトキシプロピオネート、3-メトキシブチルアセテート、3-メチル-3-メトキシブチルアセテート、蟻酸ブチル、蟻酸プロピル、乳酸エチル、乳酸ブチル、乳酸プロピル等のエステル系溶剤、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド等のアミド系溶剤、トルエン、キシレン等の芳香族炭化水素系溶剤、オクタン、デカン等の脂肪族炭化水素系溶剤が挙げられる。
特に好ましい範囲である2kPa以下の蒸気圧を有する溶剤の具体的な例としては、1-オクタノン、2-オクタノン、1-ノナノン、2-ノナノン、4-ヘプタノン、2-ヘキサノン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、フェニルアセトン等のケトン系溶剤、酢酸ブチル、酢酸アミル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチル-3-エトキシプロピオネート、3-メトキシブチルアセテート、3-メチル-3-メトキシブチルアセテート、乳酸エチル、乳酸ブチル、乳酸プロピル等のエステル系溶剤、N-メチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド等のアミド系溶剤、キシレン等の芳香族炭化水素系溶剤、オクタン、デカン等の脂肪族炭化水素系溶剤が挙げられる。
現像液には、必要に応じて1種または2種以上の界面活性剤を適当量添加することができる。
界面活性剤としては特に限定されないが、例えば、上記の水溶性樹脂組成物の項で述べた界面活性剤が好ましく用いられる。
現像液に界面活性剤を配合する場合、その配合量は現像液の全量に対して、通常0.001~5質量%であり、好ましくは0.005~2質量%であり、より好ましくは0.01~0.5質量%である。
現像方法としては、例えば、現像液が満たされた槽中に基板を一定時間浸漬する方法(ディップ法)、基板表面に現像液を表面張力によって盛り上げて一定時間静止することで現像する方法(パドル法)、基板表面に現像液を噴霧する方法(スプレー法)、一定速度で回転している基板上に一定速度で現像液吐出ノズルをスキャンしながら現像液を吐出しつづける方法(ダイナミックディスペンス法)などを適用することができる。
上記各種の現像方法が、現像装置の現像ノズルから現像液を感光層に向けて吐出する工程を含む場合、吐出される現像液の吐出圧(吐出される現像液の単位面積あたりの流速)は、好ましくは2mL/秒/mm2以下、より好ましくは1.5mL/秒/mm2以下、さらに好ましくは1mL/秒/mm2以下である。流速の下限は特に無いが、スループットを考慮すると0.2mL/秒/mm2以上が好ましい。吐出される現像液の吐出圧を上記の範囲とすることにより、現像後のレジスト残渣に由来するパターンの欠陥を著しく低減することができる。
このメカニズムの詳細は定かではないが、恐らくは、吐出圧を上記範囲とすることで、現像液が感光層に与える圧力が小さくなり、感光層上のレジストパターンが不用意に削られたり崩れたりすることが抑制されるためと考えられる。
なお、現像液の吐出圧(mL/秒/mm2)は、現像装置中の現像ノズル出口における値である。
現像液の吐出圧を調整する方法としては、例えば、ポンプなどで吐出圧を調整する方法や、加圧タンクからの供給で圧力を調整することで変える方法などを挙げることができる。
また、有機溶剤を含む現像液を用いて現像する工程の後に、他の有機溶剤に置換しながら、現像を停止する工程を実施してもよい。 << (4) Step of developing mask pattern by developing using developer containing organic solvent >>
In the step (3), the photosensitive layer is exposed through a mask and then developed using a developer containing an organic solvent (hereinafter also referred to as an organic developer). Development is preferably a negative type. Sp value of the solvent contained in the developer is preferably less than 19 MPa 1/2, and more preferably 18 MPa 1/2 or less.
As the organic solvent contained in the developer, polar solvents such as ketone solvents, ester solvents, amide solvents, and hydrocarbon solvents can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, Examples include methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Can be mentioned.
Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
The organic solvent may be used alone or in combination of two or more. Moreover, you may mix and use with organic solvents other than the above. However, the water content of the whole developer is preferably less than 10% by mass, and more preferably substantially free of moisture. The term “substantially” as used herein means, for example, that the water content of the entire developing solution is 3% by mass or less, and more preferably the measurement limit or less.
That is, the amount of the organic solvent used relative to the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developer. .
In particular, the organic developer preferably contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, and amide solvents.
The organic developer may contain an appropriate amount of a basic compound as required. Examples of the basic compound include those described in the above basic compound section.
The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and further preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Improves.
Specific examples of the solvent having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone and diisobutyl. Ketone solvents such as ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylisobutylketone, butyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol Monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, Ester solvents such as butyl acid, propyl formate, ethyl lactate, butyl lactate, propyl lactate, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, xylene And aromatic hydrocarbon solvents such as octane and decane.
Specific examples of the solvent having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, Ketone solvents such as methylcyclohexanone and phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, Ester solvents such as 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate, N-methyl-2- Pyrrolidone, N, N- dimethylacetamide, N, amide solvents such as N- dimethylformamide, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.
An appropriate amount of one or more surfactants can be added to the developer as required.
Although it does not specifically limit as surfactant, For example, surfactant described in the item of said water-soluble resin composition is used preferably.
When a surfactant is blended in the developer, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0, based on the total amount of the developer. 0.01 to 0.5% by mass.
As a development method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
When the above-mentioned various development methods include a step of discharging the developer from the developing nozzle of the developing device toward the photosensitive layer, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is , Preferably 2 mL / sec / mm 2 or less, more preferably 1.5 mL / sec / mm 2 or less, and even more preferably 1 mL / sec / mm 2 or less. There is no particular lower limit of the flow rate, but 0.2 mL / second / mm 2 or more is preferable in consideration of throughput. By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.
The details of this mechanism are not clear, but perhaps by setting the discharge pressure in the above range, the pressure applied to the photosensitive layer by the developer is reduced, and the resist pattern on the photosensitive layer is inadvertently scraped or broken. This is considered to be suppressed.
The developer discharge pressure (mL / second / mm 2 ) is a value at the developing nozzle outlet in the developing device.
Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
Moreover, you may implement the process of stopping image development, after substituting with another organic solvent after the process developed using the developing solution containing the organic solvent.
感光層を現像してマスクパターンを作製した後、エッチング処理にて少なくとも非マスク部の上記水溶性樹脂層および上記有機半導体層を除去する。非マスク部とは、上記現像工程において感光層が除去された箇所を表す。
具体的には、ドライエッチングは、レジストパターンをエッチングマスクとして、少なくとも水溶性樹脂層および有機半導体層をドライエッチングする。ドライエッチングの代表的な例としては、特開昭59-126506号公報、特開昭59-046628号公報、特開58-009108号公報、特開58-002809号公報、特開57-148706号公報、特開61-041102号公報に記載の方法がある。
ドライエッチングとしては、パターン断面をより矩形に近く形成する観点や有機半導体層へのダメージをより低減する観点から、以下の形態で行なうのが好ましい。
フッ素系ガスと酸素ガス(O2)との混合ガスを用い、有機半導体層が露出しない領域(深さ)までエッチングを行なう第1段階のエッチングと、この第1段階のエッチングの後に、窒素ガス(N2)と酸素ガス(O2)との混合ガスを用い、好ましくは有機半導体層が露出する領域(深さ)付近までエッチングを行なう第2段階のエッチングと、有機半導体層が露出した後に行なうオーバーエッチングとを含む形態が好ましい。以下、ドライエッチングの具体的手法、並びに第1段階のエッチング、第2段階のエッチング、およびオーバーエッチングについて説明する。
ドライエッチングは、下記手法により事前にエッチング条件を求めて行なう。
(1)第1段階のエッチングにおけるエッチングレート(nm/分)と、第2段階のエッチングにおけるエッチングレート(nm/分)とをそれぞれ算出する。(2)第1段階のエッチングで所望の厚さをエッチングする時間と、第2段階のエッチングで所望の厚さをエッチングする時間とをそれぞれ算出する。(3)上記(2)で算出したエッチング時間に従って第1段階のエッチングを実施する。(4)上記(2)で算出したエッチング時間に従って第2段階のエッチングを実施する。あるいはエンドポイント検出でエッチング時間を決定し、決定したエッチング時間に従って第2段階のエッチングを実施してもよい。(5)上記(3)、(4)の合計時間に対してオーバーエッチング時間を算出し、オーバーエッチングを実施する。
上記第1段階のエッチング工程で用いる混合ガスとしては、被エッチング膜である有機材料を矩形に加工する観点から、フッ素系ガスおよび酸素ガス(O2)を含むことが好ましい。また、第1段階のエッチング工程は、有機半導体層が露出しない領域までエッチングすることで、有機半導体層のダメージを回避することができる。また、上記第2段階のエッチング工程および上記オーバーエッチング工程は、第1段階のエッチング工程でフッ素系ガスおよび酸素ガスの混合ガスにより有機半導体層が露出しない領域までエッチングを実施した後、有機半導体層のダメージ回避の観点から、窒素ガスおよび酸素ガスの混合ガスを用いてエッチング処理を行なうのが好ましい。
第1段階のエッチング工程でのエッチング量と、第2段階のエッチング工程でのエッチング量との比率は、第1段階のエッチング工程でのエッチング処理による矩形性を損なわないように決定することが重要である。なお、全エッチング量(第1段階のエッチング工程でのエッチング量と第2段階のエッチング工程でのエッチング量との総和)中における後者の比率は、0%より大きく50%以下である範囲が好ましく、10~20%がより好ましい。エッチング量とは、被エッチング膜の残存する膜厚とエッチング前の膜厚との差から算出される量のことをいう。
また、エッチングは、オーバーエッチング処理を含むことが好ましい。オーバーエッチング処理は、オーバーエッチング比率を設定して行なうことが好ましい。また、オーバーエッチング比率は、初めに行なうエッチング処理時間より算出することが好ましい。オーバーエッチング比率は任意に設定できるが、フォトレジストのエッチング耐性と被エッチングパターンの矩形性維持の点で、エッチング工程におけるエッチング処理時間の30%以下であることが好ましく、5~25%であることがより好ましく、10~15%であることが特に好ましい。 << (5) Step of removing at least the non-masked water-soluble resin layer and the organic semiconductor layer by dry etching treatment >>
After developing the photosensitive layer to produce a mask pattern, at least the water-soluble resin layer and the organic semiconductor layer in the non-mask portion are removed by an etching process. The non-mask portion represents a portion where the photosensitive layer has been removed in the development process.
Specifically, in the dry etching, at least the water-soluble resin layer and the organic semiconductor layer are dry etched using the resist pattern as an etching mask. Representative examples of dry etching include Japanese Patent Application Laid-Open Nos. 59-126506, 59-046628, 58-009108, 58-002809, and 57-148706. There is a method described in Japanese Patent Laid-Open No. 61-0410102.
The dry etching is preferably performed in the following manner from the viewpoint of forming the pattern cross section closer to a rectangle and reducing damage to the organic semiconductor layer.
A first stage etching using a mixed gas of fluorine-based gas and oxygen gas (O 2 ) to perform etching up to a region (depth) where the organic semiconductor layer is not exposed, and after this first stage etching, nitrogen gas A second stage etching is performed in which a mixed gas of (N 2 ) and oxygen gas (O 2 ) is used, and etching is preferably performed to the vicinity of the region (depth) where the organic semiconductor layer is exposed, and after the organic semiconductor layer is exposed A form including overetching to be performed is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.
Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated. (2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated. (3) The first stage etching is performed according to the etching time calculated in (2) above. (4) The second stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time. (5) Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.
The mixed gas used in the first stage etching step preferably contains a fluorine-based gas and an oxygen gas (O 2 ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In the first step, the organic semiconductor layer can be prevented from being damaged by etching the region where the organic semiconductor layer is not exposed. The second-stage etching process and the over-etching process may be performed by performing etching to a region where the organic semiconductor layer is not exposed by a mixed gas of fluorine-based gas and oxygen gas in the first-stage etching process. From the viewpoint of avoiding damage, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.
It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.
Etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.
エッチング後、溶剤(通常は、水)を用いて水溶性樹脂層を除去することが好ましい。
水溶性樹脂層を水で除去する方法としては、例えば、スプレー式またはシャワー式の噴射ノズルからレジストパターンに洗浄水を噴射して、水溶性樹脂層を除去する方法を挙げることができる。洗浄水としては、純水を好ましく用いることができる。また、噴射ノズルとしては、その噴射範囲内に基板全体が包含される噴射ノズルや、可動式の噴射ノズルであってその可動範囲が基板全体を包含する噴射ノズルを挙げることができる。
噴射ノズルが可動式の場合、水溶性樹脂層を除去する工程中に基板中心部から基板端部までを2回以上移動して洗浄水を噴射することで、より効果的にレジストパターンを除去することができる。
水を除去した後、乾燥等の工程を行うことも好ましい。乾燥温度としては、80~120℃とすることが好ましい。 << (6) Step of removing water-soluble resin layer >>
After the etching, it is preferable to remove the water-soluble resin layer using a solvent (usually water).
Examples of the method for removing the water-soluble resin layer with water include a method for removing the water-soluble resin layer by spraying cleaning water onto the resist pattern from a spray type or shower type spray nozzle. As the washing water, pure water can be preferably used. Examples of the injection nozzle include an injection nozzle in which the entire substrate is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire substrate.
When the spray nozzle is movable, the resist pattern is more effectively removed by spraying the cleaning water by moving from the center of the substrate to the end of the substrate at least twice during the process of removing the water-soluble resin layer. be able to.
It is also preferable to perform a process such as drying after removing water. The drying temperature is preferably 80 to 120 ° C.
本発明の感光層は、有機半導体を利用した電子デバイスの製造に用いることができる。ここで、電子デバイスとは、半導体を含有し、かつ2つ以上の電極を有し、その電極間に流れる電流や生じる電圧を、電気、光、磁気、化学物質などにより制御するデバイス、あるいは、印加した電圧や電流により、光や電場、磁場などを発生させるデバイスである。例としては、有機光電変換素子、有機電界効果トランジスタ、有機電界発光素子、ガスセンサ、有機整流素子、有機インバータ、情報記録素子などが挙げられる。有機光電変換素子は光センサ用途、エネルギー変換用途(太陽電池)のいずれにも用いることができる。これらの中で、用途として好ましくは有機電界効果トランジスタ、有機光電変換素子、有機電界発光素子であり、より好ましくは有機電界効果トランジスタ、有機光電変換素子であり、特に好ましくは有機電界効果トランジスタである。 <Application>
The photosensitive layer of the present invention can be used for production of an electronic device using an organic semiconductor. Here, an electronic device is a device that contains a semiconductor and has two or more electrodes, and a current flowing between the electrodes and a generated voltage are controlled by electricity, light, magnetism, chemical substances, or the like, or It is a device that generates light, electric field, magnetic field, etc. by applied voltage or current. Examples include organic photoelectric conversion elements, organic field effect transistors, organic electroluminescent elements, gas sensors, organic rectifying elements, organic inverters, information recording elements, and the like. The organic photoelectric conversion element can be used for both optical sensor applications and energy conversion applications (solar cells). Among these, organic field effect transistors, organic photoelectric conversion elements, and organic electroluminescence elements are preferable as applications, more preferably organic field effect transistors and organic photoelectric conversion elements, and particularly preferably organic field effect transistors. .
樹脂のMwは国際公開第2015/098978号の段落0061-0070に記載の方法に従って測定した。 <Measurement method of weight average molecular weight (Mw)>
The Mw of the resin was measured according to the method described in paragraphs 0061-0070 of WO2015 / 098978.
<水溶性樹脂組成物の調製>
以下の処方で、各成分を混合して均一な2L溶液とした後、3M ZetaPlus EC8PI-150GN デプスフィルター(0.8μm相当)を用いてろ過して水溶性樹脂組成物を調製した。
<<PVA-1>>
下記PVA 15.0質量部
界面活性剤D-1(下記) 0.008質量部
水 84.9質量部
<PVA-1(Mw=15,000)クラレ社製 PVA-203 重合度300)
<<PVP-1>>
下記PVP 15.0質量部
界面活性剤D-1(下記) 0.008質量部
水 84.9質量部
<PVP-1(Mw=360,000)> 東京化成 ポリビニルピロリドン K90 Examples 1 to 12 and Comparative Examples 1 and 2
<Preparation of water-soluble resin composition>
In the following formulation, each component was mixed to make a uniform 2 L solution, and then filtered using a 3M ZetaPlus EC8PI-150GN depth filter (equivalent to 0.8 μm) to prepare a water-soluble resin composition.
<< PVA-1 >>
The following PVA 15.0 parts by mass Surfactant D-1 (described below) 0.008 parts by mass Water 84.9 parts by mass <PVA-1 (Mw = 15,000) Kuraray PVA-203 polymerization degree 300)
<< PVP-1 >>
PVP 15.0 parts by mass Surfactant D-1 (described below) 0.008 parts by mass Water 84.9 parts by mass <PVP-1 (Mw = 360,000)> Tokyo Kasei Polyvinylpyrrolidone K90
以下のようにして、各酸反応性樹脂を合成した。
<<酸反応性樹脂A-1の合成>>
窒素気流下、メチルイソブチルケトン8.4gを3つ口フラスコに入れ、これを80℃に加熱した。これに、メタクリル酸2-シクロヘキシルプロパン-2-イル9.4g、メタクリル酸3-ヒドロキシ-1-アダマンチル4.7g、β-メタクリロイロキシ-γ-ブチロラクトン6.8gおよびアゾビスイソブチロニトリルを全モノマー量に対して6モル%をメチルイソブチルケトン75.3gに溶解させた溶液を6時間かけて滴下した。滴下終了後、さらに80℃で2時間反応させた。反応液を放冷後ヘブタン720ml/酢酸エチル80mlに注ぎ、析出した粉体をろ取、乾燥すると、酸反応性樹脂A-1が18.3g得られた。得られた樹脂の重量平均分子量は9300、分散度(Mw/Mn)は1.98であった。 <Preparation of photosensitive resin composition>
Each acid-reactive resin was synthesized as follows.
<< Synthesis of Acid Reactive Resin A-1 >>
Under a nitrogen stream, 8.4 g of methyl isobutyl ketone was placed in a three-necked flask and heated to 80 ° C. To this, 9.4 g of 2-cyclohexylpropan-2-yl methacrylate, 4.7 g of 3-hydroxy-1-adamantyl methacrylate, 6.8 g of β-methacryloyloxy-γ-butyrolactone and azobisisobutyronitrile were added. A solution prepared by dissolving 6 mol% of methyl isobutyl ketone in 75.3 g of the total monomer amount was added dropwise over 6 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then poured into 720 ml of heptane / 80 ml of ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain 18.3 g of acid-reactive resin A-1. The obtained resin had a weight average molecular weight of 9,300 and a dispersity (Mw / Mn) of 1.98.
窒素導入管および、冷却管を取り付けた200mL三口フラスコにPGMEA(プロピレングリコールモノメチルエーテルアセテート)(32.62g)を入れ、86℃に昇温した。ここに、BzMA(16.65g)、THFMA(21.08g)、t-BuMA(5.76g)、およびV-601(0.4663g)をPGMEA(32.62g)に溶解したものを2時間かけて滴下した。その後、反応液を2時間撹拌し、反応を終了させた。反応液をヘプタン中に再沈することで生じた白色粉体をろ過により回収することで、酸反応性樹脂A-2を得た。重量平均分子量(Mw)は45,000であった。
Mwが1,000以下の成分の量は、3質量%であった。 << Synthesis of Acid Reactive Resin A-2 >>
PGMEA (propylene glycol monomethyl ether acetate) (32.62 g) was placed in a 200 mL three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. Here, BzMA (16.65 g), THFMA (21.08 g), t-BuMA (5.76 g), and V-601 (0.4663 g) dissolved in PGMEA (32.62 g) were taken over 2 hours. And dripped. Thereafter, the reaction solution was stirred for 2 hours to complete the reaction. The white powder produced by reprecipitation of the reaction solution in heptane was collected by filtration to obtain acid-reactive resin A-2. The weight average molecular weight (Mw) was 45,000.
The amount of the component having Mw of 1,000 or less was 3% by mass.
ポリヒドロキシスチレン化合物としてのポリ(p-ヒドロキシスチレン)(VP-2500,日本曹達株式会社製)30gをPGMEA120gに溶解した。この溶液に、ビニルエーテル化合物として2-シクロヘキシルエチルビニルエーテル10.40gおよび1.45gの2質量%カンファースルホン酸(PGMEA溶液)を加え、室温で2時間撹拌した。1.05gの10質量%トリエチルアミン(PGMEA溶液)を加え、しばらく撹拌した後、反応液を酢酸エチル165mLの入った分液ロートに移した。この有機層を蒸留水200mLで3回洗浄後、エバポレーターで酢酸エチルを除去した。得られた反応液を2Lのヘキサン中に滴下し、上澄みを除去した。得られた生成物をPGMEA95gに溶解し、減圧条件で低沸点溶媒を除去することで、酸反応性樹脂A-3のPGMEA溶液(28.3質量%)が132.3g得られた。平均分子量(Mw)は5,400および分散度(Mw/Mn)は1.1であった。 << Synthesis of Acid-Reactive Resin A-3 >>
30 g of poly (p-hydroxystyrene) (VP-2500, manufactured by Nippon Soda Co., Ltd.) as a polyhydroxystyrene compound was dissolved in 120 g of PGMEA. To this solution, 10.40 g of 2-cyclohexylethyl vinyl ether and 1.45 g of 2% by mass camphorsulfonic acid (PGMEA solution) were added as a vinyl ether compound, and the mixture was stirred at room temperature for 2 hours. 1.05 g of 10% by mass triethylamine (PGMEA solution) was added and stirred for a while, and then the reaction solution was transferred to a separatory funnel containing 165 mL of ethyl acetate. This organic layer was washed three times with 200 mL of distilled water, and then ethyl acetate was removed with an evaporator. The obtained reaction solution was dropped into 2 L of hexane, and the supernatant was removed. The obtained product was dissolved in 95 g of PGMEA, and the low boiling point solvent was removed under reduced pressure conditions to obtain 132.3 g of a PGMEA solution (28.3 mass%) of acid-reactive resin A-3. The average molecular weight (Mw) was 5,400 and the dispersity (Mw / Mn) was 1.1.
円形のガラス基板上に、以下の組成からなる有機半導体塗布液(有機半導体形成用組成物)をスピンコートし、130℃で10分乾燥させることで有機半導体層を形成した。膜厚は150nmであった。 <Production of organic semiconductor substrate>
An organic semiconductor coating liquid (composition for forming an organic semiconductor) having the following composition was spin-coated on a circular glass substrate and dried at 130 ° C. for 10 minutes to form an organic semiconductor layer. The film thickness was 150 nm.
P3HT(シグマ アルドリッチ ジャパン合同会社製) 10質量%
PCBM(シグマ アルドリッチ ジャパン合同会社製) 10質量%
クロロホルム(富士フイルム和光純薬(株)製) 80質量% << Composition of organic semiconductor coating liquid >>
P3HT (Sigma Aldrich Japan GK) 10% by mass
PCBM (Sigma Aldrich Japan GK) 10% by mass
Chloroform (Fujifilm Wako Pure Chemical Industries, Ltd.) 80% by mass
上記有機半導体層の表面に、水溶性樹脂組成物をスピンコートし、100℃で1分乾燥させることで、厚さ2.0μmの水溶性樹脂層を形成した。 <Formation of water-soluble resin layer>
A water-soluble resin composition was spin-coated on the surface of the organic semiconductor layer and dried at 100 ° C. for 1 minute to form a water-soluble resin layer having a thickness of 2.0 μm.
製膜した水溶性樹脂層の表面に、感光性樹脂組成物をスピンコートし、100℃で1分間乾燥(プリベーク)し、感光層を形成した。膜厚は2.0μmであった。次に、i線またはKrF線の平行露光機を用い、所定のマスクを介して、表1に示すi線を、80mJとなるように照射して、表1に示す露光量となるように露光した。その後、表1に示す条件でポストベーク(PEB)し、酢酸ブチルで表1に示す現像処理時間で現像することでマスクパターンを得た。上記露光および現像によって、酸発生剤がi線またはKrF線の照射によって酸を発生し、上記酸の発生により、実施例6以外は酢酸ブチルに対する溶解度が低下し、実施例6は酢酸ブチルに対する溶解速度が上昇したことを確認した。 <Formation of photosensitive layer>
A photosensitive resin composition was spin-coated on the surface of the water-soluble resin layer thus formed, and dried (prebaked) at 100 ° C. for 1 minute to form a photosensitive layer. The film thickness was 2.0 μm. Next, using a parallel exposure machine of i-line or KrF line, the i-line shown in Table 1 is irradiated to 80 mJ through a predetermined mask, and exposure is performed so that the exposure amount shown in Table 1 is obtained. did. Thereafter, post-baking (PEB) was performed under the conditions shown in Table 1, and development was performed with butyl acetate for the development processing time shown in Table 1 to obtain a mask pattern. By the exposure and development, the acid generator generates an acid by irradiation with i-line or KrF-ray, and the generation of the acid reduces the solubility in butyl acetate except for Example 6, and Example 6 is soluble in butyl acetate. It was confirmed that the speed increased.
感光性樹脂組成物中の水分量は以下の方法により測定した。
平沼自動水分測定装置 AQV-2200を用いて、組成物重量中の水分量を算出した。 <Measurement of water content>
The moisture content in the photosensitive resin composition was measured by the following method.
Using the Hiranuma automatic moisture analyzer AQV-2200, the moisture content in the composition weight was calculated.
感光性樹脂組成物中のナトリウムイオン、カリウムイオンおよびカルシウムイオンの合計含有量の測定は、以下の方法にて行った。
高周波誘導結合プラズマ質量分析計(ICP-MS- Inductively Coupled Plasma Mass Spectrometer:Agilent Technologies製7500cs)により、Na、K、Caを金属分析して求めた。得られた金属濃度の値は重合体濃度で除して重合体固形分換算の金属濃度(金属不純物含有量)を算出した。 <Measurement of metal ion content>
The total content of sodium ions, potassium ions and calcium ions in the photosensitive resin composition was measured by the following method.
Na, K, and Ca were obtained by metal analysis using a high-frequency inductively coupled plasma mass spectrometer (ICP-MS-Inductively Coupled Plasma Mass Spectrometer: 7500 cs manufactured by Agilent Technologies). The obtained metal concentration value was divided by the polymer concentration to calculate the metal concentration (metal impurity content) in terms of polymer solid content.
PVA膜(製造元:日本酢ビポバール製、品番:PXP-05)に対する、静止接触角の測定は下記のようにして行った。静止接触角は図2に示した基板22に対する液滴21の角度Θを測定した。
静止接触角計(協和界面科学社製)を用い、シリンジで、液滴サイズ10μLの水滴を着滴させ、23℃で着滴10秒後の接触角を測定した。 <Measurement of static contact angle>
The measurement of the static contact angle with respect to the PVA membrane (manufacturer: Nippon Vinegar Bipovar, product number: PXP-05) was performed as follows. As the static contact angle, the angle Θ of the
Using a static contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.), a water droplet with a droplet size of 10 μL was deposited with a syringe, and the contact angle after 10 seconds of deposition was measured at 23 ° C.
13mm角の露光領域を8インチウェハ上に露光し(1インチは2.54cmである)、露光後ベーク(PEB)を行い、酢酸ブチルを用いて有機溶剤現像を行った。13mm角の開口部内のディフェクト数を欠陥検査装置COMPLUS 3T(AMAT社製)にて、5000nm以上の長さを有する欠陥を残渣として、その個数を確認した。評価は10か所の測定値の平均値で行った。有機系のディフェクトと無機系のディフェクトについてそれぞれ測定し評価した。ディフェクトのうち、特徴的な核のある欠陥残渣の形状を、SEM VISION G4(AMAT製)で観察し、さらにエネルギー分散型X線分析(EDX)により金属成分の有無を解析した。残渣のうち、金属成分が検出されたものを金属系残渣とし、それ以外を有機系残渣とした。
ここで有機系残渣とは、少なくとも炭素原子と酸素原子とが検出され、金属成分が検出されない硬化膜の表面の欠陥をいい、金属系残渣とは、少なくとも炭素原子と酸素原子と、少なくとも1種の金属成分とが検出される硬化膜の表面の欠陥である。両者のうち低い結果を各試験の総合評価とした。
レジスト開口部の残渣の個数
A=0.5個/cm2未満
B=0.5~0.8個/cm2
C=0.8個/cm2以上 <Defects>
A 13 mm square exposure area was exposed on an 8-inch wafer (1 inch is 2.54 cm), post-exposure baking (PEB) was performed, and organic solvent development was performed using butyl acetate. The number of defects in the opening of 13 mm square was confirmed by a defect inspection apparatus COMPLUS 3T (manufactured by AMAT), with a defect having a length of 5000 nm or more as a residue. Evaluation was performed by the average value of the measured values at 10 locations. Each of the organic defects and the inorganic defects was measured and evaluated. Among the defects, the shape of defect residues having characteristic nuclei was observed with SEM VISION G4 (manufactured by AMAT), and the presence or absence of metal components was analyzed by energy dispersive X-ray analysis (EDX). Among the residues, those in which the metal component was detected were defined as metal residues, and the others were defined as organic residues.
Here, the organic residue means a defect on the surface of the cured film in which at least carbon atoms and oxygen atoms are detected but no metal component is detected. The metal residue means at least one of carbon atoms and oxygen atoms. This is a defect of the surface of the cured film in which the metal component is detected. The lower result of both was taken as the overall evaluation of each test.
Number of residues in resist opening A = less than 0.5 / cm 2 B = 0.5 to 0.8 / cm 2
C = 0.8 / cm 2 or more
B-1 下記式OS-107において、R11=トルイル基、R18=メチル基である化合物を採用した。
B-1 A compound in which R11 = toluyl group and R18 = methyl group in the following formula OS-107 was employed.
C-1 下記式で示されるチオ尿素誘導体である
C-1 is a thiourea derivative represented by the following formula
E-1:プロピレングリコールモノメチルエーテルアセテート(PGMEA) <Solvent>
E-1: Propylene glycol monomethyl ether acetate (PGMEA)
2 水溶性樹脂層
3 有機半導体層
4 基板
5 除去部
9 ディフェクト
11 従来の感光層
22 被試験体(基板)
21 試料液滴
Θ 静止接触角 DESCRIPTION OF
21 Sample droplet Θ Static contact angle
Claims (14)
- 水溶性樹脂層と感光層とを有する積層体に含まれる感光層であって、
前記感光層は、活性光線および放射線の少なくとも一方の照射により酸を発生する化合物と、酸の作用により酢酸ブチルに対する溶解速度が変化する樹脂と、水とを含む感光性樹脂組成物から形成された層であり、前記感光性樹脂組成物中の水の含有量が0.008質量%以上1質量%以下である、感光層。 A photosensitive layer included in a laminate having a water-soluble resin layer and a photosensitive layer,
The photosensitive layer was formed from a photosensitive resin composition containing a compound that generates an acid upon irradiation with at least one of actinic rays and radiation, a resin whose dissolution rate in butyl acetate is changed by the action of an acid, and water. A photosensitive layer, which is a layer and has a water content in the photosensitive resin composition of 0.008% by mass or more and 1% by mass or less. - 前記感光層がi線の照射に対して感光能を有する、請求項1に記載の感光層。 The photosensitive layer according to claim 1, wherein the photosensitive layer has photosensitivity to i-ray irradiation.
- ポリビニルアルコール膜上における前記感光性樹脂組成物の静止接触角が2°以上60°以下である、請求項1または2に記載の感光層。 The photosensitive layer according to claim 1 or 2, wherein a static contact angle of the photosensitive resin composition on the polyvinyl alcohol film is 2 ° or more and 60 ° or less.
- 前記感光層における樹脂の酸の作用による溶解速度の変化が溶解速度の低下である、請求項1~3のいずれか1項に記載の感光層。 The photosensitive layer according to any one of claims 1 to 3, wherein a change in dissolution rate due to the action of an acid of the resin in the photosensitive layer is a decrease in dissolution rate.
- 前記感光層における樹脂が下記式(1)で表される構成単位を有するポリマーを含む、請求項1~4のいずれか1項に記載の感光層;
- 前記感光性樹脂組成物中のナトリウムイオン、カリウムイオンおよびカルシウムイオンの合計含有量が1質量ppt~1000質量ppbである、請求項1~5のいずれか1項に記載の感光層。 6. The photosensitive layer according to claim 1, wherein a total content of sodium ion, potassium ion and calcium ion in the photosensitive resin composition is 1 mass ppt to 1000 mass ppb.
- 有機半導体層加工用である、請求項1~6のいずれか1項に記載の感光層。 The photosensitive layer according to any one of claims 1 to 6, which is used for processing an organic semiconductor layer.
- 請求項1~7のいずれか1項に記載の感光層と水溶性樹脂層とを有する積層体。 A laminate comprising the photosensitive layer according to any one of claims 1 to 7 and a water-soluble resin layer.
- さらに、有機半導体層を有し、前記有機半導体層、前記水溶性樹脂層、前記感光層の順に積層している、請求項8に記載の積層体。 The laminate according to claim 8, further comprising an organic semiconductor layer, wherein the organic semiconductor layer, the water-soluble resin layer, and the photosensitive layer are laminated in this order.
- 感光層を形成するための感光性樹脂組成物であって、
前記感光層は水溶性樹脂層と組み合わせて積層体をなす層であり、
活性光線および放射線の少なくとも一方の照射により酸を発生する化合物と、酸の作用により酢酸ブチルに対する溶解速度が変化する樹脂と、水とを含み、前記感光性樹脂組成物中の水の含有量が0.008質量%以上1質量%以下である、感光性樹脂組成物。 A photosensitive resin composition for forming a photosensitive layer,
The photosensitive layer is a layer that forms a laminate in combination with a water-soluble resin layer,
A compound that generates an acid upon irradiation with at least one of actinic rays and radiation, a resin that changes the dissolution rate in butyl acetate by the action of the acid, and water, and the water content in the photosensitive resin composition is The photosensitive resin composition which is 0.008 mass% or more and 1 mass% or less. - 有機半導体層加工用である、請求項10に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 10, which is used for processing an organic semiconductor layer.
- 水溶性樹脂層と感光層とをこの順に形成するためのキットであって、請求項10または11に記載の感光性樹脂組成物と水溶性樹脂組成物とを有するキット。 A kit for forming a water-soluble resin layer and a photosensitive layer in this order, comprising the photosensitive resin composition according to claim 10 or 11 and a water-soluble resin composition.
- 有機半導体層加工用である、請求項12に記載のキット。 The kit according to claim 12, which is used for processing an organic semiconductor layer.
- 活性光線および放射線の少なくとも一方の照射により酸を発生する化合物と、酸の作用により酢酸ブチルに対する溶解速度が変化する樹脂を含む組成物の水分量の少なくとも一方を調節することを含む、あるいは、
活性光線および放射線の少なくとも一方の照射により酸を発生する化合物と、酸の作用により酢酸ブチルに対する溶解速度が変化する樹脂を含む組成物に含まれる原料の水分量を調節することを含む、請求項10または11に記載の感光性樹脂組成物の製造方法。 Adjusting at least one of the water content of the composition comprising a compound that generates an acid upon irradiation with at least one of actinic rays and radiation, and a resin that changes the dissolution rate in butyl acetate by the action of the acid, or
The method includes adjusting a moisture content of a raw material contained in a composition containing a compound that generates an acid upon irradiation with at least one of actinic rays and radiation, and a resin whose dissolution rate in butyl acetate is changed by the action of the acid. The manufacturing method of the photosensitive resin composition of 10 or 11.
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JP2012058304A (en) * | 2010-09-06 | 2012-03-22 | Asahi Kasei E-Materials Corp | Photosensitive resin composition, cured relief pattern and semiconductor device |
JP2014098889A (en) * | 2012-10-19 | 2014-05-29 | Fujifilm Corp | Resin composition for forming protective film, protective film, pattern forming method, method for manufacturing electronic device, and electronic device |
WO2016175220A1 (en) * | 2015-04-28 | 2016-11-03 | 富士フイルム株式会社 | Laminate and kit |
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JP6284849B2 (en) | 2013-08-23 | 2018-02-28 | 富士フイルム株式会社 | Laminate |
JP6167016B2 (en) * | 2013-10-31 | 2017-07-19 | 富士フイルム株式会社 | Laminate, organic semiconductor manufacturing kit and organic semiconductor manufacturing resist composition |
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2019
- 2019-02-19 TW TW108105355A patent/TW201936673A/en unknown
- 2019-02-21 CN CN201980013984.8A patent/CN111758074A/en active Pending
- 2019-02-21 KR KR1020207023864A patent/KR20200110399A/en not_active Application Discontinuation
- 2019-02-21 WO PCT/JP2019/006427 patent/WO2019163859A1/en active Application Filing
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US20050221219A1 (en) * | 2004-03-31 | 2005-10-06 | Wang Yueh | Resist compounds including acid labile groups attached to polymeric chains at anhydride linkages |
JP2006343704A (en) * | 2004-09-28 | 2006-12-21 | Jsr Corp | Positive-radiation-sensitive resin composition |
JP2006243293A (en) * | 2005-03-02 | 2006-09-14 | Jsr Corp | Radiation-sensitive resin composition |
JP2011169980A (en) * | 2010-02-16 | 2011-09-01 | Asahi Kasei E-Materials Corp | Photosensitive resin composition, method for manufacturing cured relief pattern, and semiconductor device |
JP2012058304A (en) * | 2010-09-06 | 2012-03-22 | Asahi Kasei E-Materials Corp | Photosensitive resin composition, cured relief pattern and semiconductor device |
JP2014098889A (en) * | 2012-10-19 | 2014-05-29 | Fujifilm Corp | Resin composition for forming protective film, protective film, pattern forming method, method for manufacturing electronic device, and electronic device |
WO2016175220A1 (en) * | 2015-04-28 | 2016-11-03 | 富士フイルム株式会社 | Laminate and kit |
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JPWO2019163859A1 (en) | 2021-02-04 |
KR20200110399A (en) | 2020-09-23 |
CN111758074A (en) | 2020-10-09 |
TW201936673A (en) | 2019-09-16 |
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